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A 高分子化学和高分子物理 UNIT 1 What are Polymer? 第一单元 什么是高聚物?

What are polymers? For one thing, they are complex and giant molecules and are different from low molecular weight compounds like, say, common salt. To contrast the difference, the molecular weight of common salt is only 58.5, while that of a polymer can be as high as several hundred thousand, even more than thousand thousands. These big molecules or ‘macro-molecules’ are made up of much smaller molecules, can be of one or more chemical compounds. To illustrate, imagine that a set of rings has the same size and is made of the same material. When these things are interlinked, the chain formed can be considered as representing a polymer from molecules of the same compound. Alternatively, individual rings could be of different sizes and materials, and interlinked to represent a polymer from molecules of different compounds.

什么是高聚物?首先,他们是合成物和大分子,而且不同于低分子化合物,譬如说普通的盐。与低分子化合物不同的是,普通盐的分子量仅仅是58.5,而高聚物的分子量高于105,甚至大于106。这些大分子或“高分子”由许多小分子组成。小分子相互结合形成大分子,大分子能够是一种或多种化合物。举例说明,想象一组大小相同并由相同的材料制成的环。当这些环相互连接起来,可以把形成的链看成是具有同种分子量化合物组成的高聚物。另一方面,独特的环可以大小不同、材料不同,相连接后形成具有不同分子量化合物组成的聚合物。 This interlinking of many units has given the polymer its name, poly meaning ‘many’ and mer meaning ‘part’ (in Greek). As an example, a gaseous compound called butadiene, with a molecular weight of 54, combines nearly 4000 times and gives a polymer known as polybutadiene (a synthetic rubber) with about 200 000molecular weight. The low molecular weight compounds from which the polymers form are known as monomers. The picture is simply as follows:

许多单元相连接给予了聚合物一个名称,poly意味着“多、聚、重复”,mer意味着“链节、基体”(希腊语中)。例如:称为丁二烯的气态化合物,分子量为54,化合将近4000次,得到分子量大约为200000被称作聚丁二烯(合成橡胶)的高聚物。形成高聚物的低分子化合物称为单体。下面简单地描述一下形成过程:

butadiene + butadiene + ??? + butadiene--→polybutadiene (4 000 time)

丁二烯 +丁二烯+…+丁二烯——→聚丁二烯 (4000次)

One can thus see how a substance (monomer) with as small a molecule weight as 54 grow to become a giant molecule (polymer) of (54×4 000≈)200 000 molecular weight.

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It is essentially the ‘giantness’ of the size of the polymer molecule that makes its behavior different from that of a commonly known chemical compound such as benzene. Solid benzene, for instance, melts to become liquid benzene at 5.5℃ and , on further heating, boils into gaseous benzene. As against this well-defined behavior of a simple chemical compound, a polymer like polyethylene does not melt sharply at one particular temperature into clean liquid. Instead, it becomes increasingly softer and, ultimately, turns into a very viscous, tacky molten mass. Further heating of this hot, viscous, molten polymer does convert it into various gases but it is no longer polyethylene. (Fig. 1.1) .

因而能够看到分子量仅为54的小分子物质(单体)如何逐渐形成分子量为200000的大分子(高聚物)。实质上,正是由于聚合物的巨大的分子尺寸才使其性能不同于象苯这样的一般化合物。例如,固态苯,在5.5℃熔融成液态苯,进一步加热,煮沸成气态苯。与这类简单化合物明确的行为相比,像聚乙烯这样的聚合物不能在某一特定的温度快速地熔融成纯净的液体。而聚合物变得越来越软,最终,变成十分粘稠的聚合物熔融体。将这种热而粘稠的聚合物熔融体进一步加热,不会转变成各种气体,但它不再是聚乙烯(如图1.1)。 固态苯——→液态苯——→气态苯 加热,5.5℃ 加热,80℃

固体聚乙烯——→熔化的聚乙烯——→各种分解产物-但不是聚乙烯 加热 加热

图1.1 低分子量化合物(苯)和聚合物(聚乙烯)受热后的不同行为

Another striking difference with respect to the behavior of a polymer and that of a low molecular weight compound concerns the dissolution process. Let us take, for example, sodium chloride and add it slowly to s fixed quantity of water. The salt, which represents a low molecular weight compound, dissolves in water up to s point (called saturation point) but, thereafter, any further quantity added does not go into solution but settles at the bottom and just remains there as solid. The viscosity of the saturated salt solution is not very much different from that of water. But if we take a polymer instead, say, polyvinyl alcohol, and add it to a fixed quantity of water, the polymer does not go into solution immediately. The globules of polyvinyl alcohol first absorb water, swell and get distorted in shape and after a long time go into solution. Also, we can add a very large quantity of the polymer to the same quantity of water without the saturation point ever being reached. As more and more quantity of polymer is added to water, the time taken for the dissolution of the polymer obviously increases and the mix ultimately assumes a soft, dough-like consistency. Another peculiarity is that, in water, polyvinyl alcohol never retains its original powdery nature as the excess sodium chloride does in a saturated salt solution. In conclusion, we can say that (1) the long time taken by polyvinyl alcohol for dissolution, (2) the absence of a

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saturation point, and (3) the increase in the viscosity are all characteristics of a typical polymer being dissolved in a solvent and these characteristics are attributed mainly to the large molecular size of the polymer. The behavior of a low molecular weight compound and that of a polymer on dissolution are illustrated in Fig.1.2.

发现另一种不同的聚合物行为和低分子量化合物行为是关于溶解过程。例如,让我们研究一下,将氯化钠慢慢地添加到固定量的水中。盐,代表一种低分子量化合物,在水中达到点(叫饱和点)溶解,但,此后,进一步添加盐不进入溶液中却沉到底部而保持原有的固体状态。饱和盐溶液的粘度与水的粘度不是十分不同,但是,如果我们用聚合物替代,譬如说,将聚乙烯醇添加到固定量的水中,聚合物不是马上进入到溶液中。聚乙烯醇颗粒首先吸水溶胀,发生形变,经过很长的时间以后进入到溶液中。同样地,我们可以将大量的聚合物加入到同样量的水中,不存在饱和点。将越来越多的聚合物加入水中,认为聚合物溶解的时间明显地增加,最终呈现柔软像面团一样粘稠的混合物。另一个特点是,在水中聚乙烯醇不会像过量的氯化钠在饱和盐溶液中那样能保持其初始的粉末状态。总之,我们可以讲(1)聚乙烯醇的溶解需要很长时间,(2)不存在饱和点,(3)粘度的增加是典型聚合物溶于溶液中的特性,这些特性主要归因于聚合物大分子的尺寸。如图1.2说明了低分子量化合物和聚合物的溶解行为。

氯化钠晶体加入到水中——→晶体进入到溶液中.溶液的粘度不是十分不同于 充分搅拌

水的粘度——→形成饱和溶液.剩余的晶体维持不溶解状态. 加入更多的晶体并搅拌 氯化钠的溶解

聚乙烯醇碎片加入到水中——→碎片开始溶胀——→碎片慢慢地进入到溶液中 允许维持现状 充分搅拌

——→形成粘稠的聚合物溶液.溶液粘度十分高于水的粘度 继续搅拌 聚合物的溶解

图1.2 低分子量化合物(氯化钠)和聚合物(聚乙烯醇)不同的溶解行为

——Gowariker VR, Viswanathan N V, Sreedhar J. Polymer Science. New York: John Wiley & Sons, 1986.6 UNIT 2 Chain Polymerization 第二单元 链式聚合反应

Many olefinic and vinyl unsaturated compounds are able to form chain-0like macromolecules through elimination of the double bond, a phenomenon first recognized by Staudinger. Diolefins polymerize in the same manner, however, only one of the two double bonds is eliminated. Such reactions occur through the initial addition of a monomer molecule to an initiator radical or an initiator ion, by which the active state is transferred from the initiator to the added monomer.

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