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When one speaks of the molecular weight of a polymer, one means something quite different from that which applies to small-sized compounds.
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Polymers differ from the small-sized compounds in that they are polydisperse or heterogeneous in molecular weight.
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Polymers, in their purest form, are mixture of molecules of different molecular weights.
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The reason for the polydispersity of polymers lies in the statistical variations present in the polymerization processes.
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When one discusses the molecular weight of a polymer, one is actually involved with its average molecular weight.
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Both the average molecular weight and the exact distribution of different molecular weights within a polymer are required in order to fully characterize it.
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The control of molecular weight and molecular weight distribution (MWD) is often used to obtain and improve certain desired physical properties in a polymer product. ΪÁË»ñµÃºÍ¸ÄÉÆ¾ÛºÏÎï²úÆ·µÄijЩÀíÏëµÄÎïÀíÐÔÖÊ£¬ÎÒÃǾ³£ÐèÒª¿ØÖÆ·Ö×ÓÁ¿ºÍ·Ö×ÓÁ¿·Ö²¼¡£
Various methods are available for the experimental measurement of the average molecular weight of a polymer sample.
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These include methods based on colligative properties, light scattering, viscosity, ultracentrifugation, and sedimentation.
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Different average molecular weights are obtained because the properties being measured are biased different toward the different sized polymer molecules in a polymer
sample.
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Some methods are biased toward the larger sized polymer molecules, while other methods are biased toward the smaller sized molecules. һЩ·½·¨¶Ô½Ï´ó³ß´çµÄ¾ÛºÏÎï·Ö×ÓÓÐÆ«²î£¨ÇãÏòÐÔ£©£¬¶øÁíÍâһЩ·½·¨Ôò¶Ô½ÏС³ß´çµÄ¾ÛºÏÎï·Ö×ÓÓÐÆ«²î£¨ÇãÏòÐÔ£©¡£
The result is that the average molecular weights obtained are correspondingly biased toward the larger or smaller sized molecules.
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The most important average molecular weights which are determined are the number-average molecular weight Mn, the weight-average molecular weight Mw and the viscosity-average molecular weight Mv.¡£
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A variety of different fractionation methods are used to determine the molecular weight distribution of a polymer sample.
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These are based on fractionation of a polymer sample using properties, such as solubility and permeability, which vary with molecular weight.
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UNIT 7 Polymer Solution
Dissolving a polymer is a slow process that occurs in two stages. Èܽâ¸ß·Ö×ÓÐèÒªÒ»¸ö»ºÂýµÄ¹ý³Ì£¬Õâ¸ö¹ý³Ì·ÖÁ½²½·¢Éú¡£
First, solvent molecules slowly diffuse into the polymer to produce a swollen gel. ÈܼÁ·Ö×Ó»ºÂýµØÀ©É¢µ½¸ß·Ö×ÓÖвúÉúÈÜÕÍÄý½º¡£
This may be all that happens if£¬for example£¬the polymer-polymer intermolecular forces are high because of crosslinking£¬crystallinity¡¤or strong hydrogen bonding. ÀýÈç, Èç¹ûÒò½»Áª£¬½á¾§ºÍºÜÇ¿µÄÇâ¼ü¶øÐγɺܴóµÄ·Ö×Ó¼äÁ¦£¬(¾ÛºÏÎïµÄÈܽâ¹ý³Ì)ÓпÉÄܾÍֻͣÁôÔÚÕâÒ»½×¶Î¡£
But if these forces can be overcome by the introduction of strong polymer-solvent interactions, the second stage of solution can take place.
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Only this stage can be materially speeded by agitation. Ö»ÓÐÕâ¸ö½×¶Î¿ÉÒÔͨ¹ý½Á°èµÃµ½Ã÷ÏÔ´Ù½ø¡£
Even so, the solution process can be quite slow (days or weeks) for materials of very
high molecular weight.
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In turn£¬the presence or absence of solubility as conditions(such as the nature of the solvent£¬or the temperature)are varied can give much information about the polymer. µ±Ìõ¼þ(ÈܼÁµÄÐÔÖÊ»òζÈ)±ä»¯µÄʱºò£¬ÓÐÎÞÈܽâÐÔÓÖ¿ÉÌṩ³öÐí¶à¹ØÓÚÕâÖÖ¾ÛºÏÎïµÄÐÅÏ¢¡£
As specified in the literature£¬the arrangements of the polymer chain differing by reason of rotations about single bands are termed conformations. ÕýÈçÔÚÎÄÏ×ÖÐËù¶¨ÒåµÄÄÇÑù£¬ÓÉÓÚÎ§ÈÆ×ŵ¥¼üµÄÐýת¶øµ¼ÖµľۺÏÎïÁ´²»Í¬µÄ¿Õ¼äÅŲ¼½Ð×ö¹¹Ïó¡£
In solution, a polymer molecule is a randomly coiling mass most of whose conformations occupy*¡®okjupai+ many times the volume of its segments alone.
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The size of the molecular coil is very much influenced by the polymer-solvent interaction forces.
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In a thermodynamically ¡°good¡± solvent, where polymer-solvent contacts are highly favored, the coils are relatively extended.
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It is the purpose to describe the conformational properties of both ideal and real polymer chains.
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The importance of the random-coil nature of the dissolved, molten, amorphous, and glassy states of high polymers cannot be overemphasized.
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Many important physical as well as thermodynamic properties of high polymers result from this characteristic structural feature.
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The random coil(Fig. 7. 1) arises from the relative freedom of rotation associated with the chain bonds of most polymers and the formidably large number of conformations accessible to the molecule.
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One of these conformations, the fully extended chain has special interest because its length, the contour length of the chain, can be calculated in a straightforward way.
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In all other cases the size of the random coil must be expressed in terms of statistical parameters such as the root-mean-square distance between its ends, (r2)1/2, or its radius of gyration, the root-mean-square distance of the elements of the chain from its center of gravity, (s2)1/2.
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For linear polymers that are not appreciably extended beyond their most probable shape, the mean-square end-to-end distance and the square of the radius of gyration are simply related:r2=6s2. For extended chains r2>6s2.
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The use of the radius of gyration is sometimes preferred because it can be determined experimentally.
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UNIT 8 Morphology of Solid Polymers
Solid polymers differ from ordinary, low molecular weight compounds in the nature of their physical state or morphology.
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Most polymers simultaneously show the characteristics of both crystalline solids and highly viscous liquids.
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X-ray and electron diffraction patterns often show the sharp features typical of three-dimensionally ordered£¬crystalline materials as well as the diffuse features materials characteristic of liquids.
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The fringed-micelle theory, developed in the 1930¡¯s, considers polymer to consist of small-sized, ordered crystalline regions-termed crystallities-imbedded in an unordered, amorphous polymer matrix.
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Polymer molecules are considered to pass through several different crystalline regions with crystallites being formed when segments from different polymer chains are precisely aligned together and undergo crystallization.
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Each polymer chain can contribute ordered segments to several crystallities. ÿ¸ö¾ÛºÏÎïÁ´¿ÉÒÔÌṩ¹æÔòÁ´¶Îµ½¼¸¸ö΢¾§¡£
The segments of the chain in between the crystallites make up the unordered amorphous matrix. This concept of polymer crystallinity is shown in Fig. 7.1.
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The folded-chain lamella theory arose in the late 1950¡¯s when polymer single crystals in the form of thin platelets termed lamella were grown form polymer solutions.
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The diffraction patterns of these single crystals indicate that the polymer molecules fold back and forth on themselves like in an accordion in the process of crystallization (Fig. 7.2).
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Semi-crystalline polymers are considered by advocates of the folded-chain theory to be chain-folded crystal with varying amounts of defects.
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The crystallinity of polymers is pictured as being completely similar to that of low molecular weight compounds.
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The defects in the chain folded crystals may be imperfect folds, irregularities in packing, chain entanglements, loose chain ends, dislocations, occluded impurities, or numerous other imperfections.
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The fringed-micelle and folded-chain theories of polymer crystallinity are often considered to be mutually exclusive but they need not be so considered.
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The folded chain theory is especially well suited for highly crystalline polymers where one can consider them to be one phase crystalline systems with defects. ÕÛµþÁ´ÀíÂÛÌØ±ðÊÊÓÃÓڸ߽ᾧ¾ÛºÏÎ¸ß½á¾§¾ÛºÏÎï±»ÈÏΪÊǾßÓÐȱÏݵĵ¥Ïà½á¾§Ìåϵ¡£
Polymers with medium to low crystallinity can often be advantageously treated by the fringed micellel concept as two phase systems composed of crystallites imbedded in uncrystallized£¬amorphous polymer.