高分子材料工程专业英语第二版课文翻译基本全了.doc

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.

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

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.

In the same way by means of a chain reaction, one monomer molecule after the other is added (2000~20000 monomers per second) until the active state is terminated through a different type of reaction. The polymerization is a chain reaction in two ways: because of the reaction kinetic and because as a reaction product one obtains a chain molecule. The length of the chain molecule is proportional to the kinetic chain length.

Staudinger第一个发现一例现象，许多烯烃和不饱和烯烃通过打开双键可以形成链式大分子。二烯烃以同样的方式聚合，然而，仅限于两个双键中的一个。这类反应是通过单体分子首先加成到引发剂自由基或引发剂离子上而进行的，靠这些反应活性中心由引发剂转移到被加成的单体上。以同样的方式，借助于链式反应，单体分子一个接一个地被加成（每秒2000～20000个单体）直到活性中心通过不同的反应类型而终止。聚合反应是链式反应的原因有两种：因为反应动力学和因为作为反应产物它是一种链式分子。链分子的长度与动力学链长成正比。

One can summarize the process as follow (R. is equal to the initiator radical): 链式反应可以概括为以下过程（R·相当与引发剂自由基）：略

One thus obtains polyvinylchloride from vinylchloride, or polystyrene from styrene, or polyethylene from ethylene, etc.

因而通过上述过程由氯乙烯得到聚氯乙烯，或由苯乙烯获得聚苯乙烯，或乙烯获得聚乙烯，等等。

The length of the chain molecules, measured by means of the degree of polymerization, can be varied over a large range through selection of suitable reaction conditions. Usually, with commercially prepared and utilized polymers, the degree of polymerization lies in the range of 1000 to 5000, but in many cases it can be below 500 and over 10000. This should not be interpreted to mean that all molecules of a certain polymeric material consist of 500, or 1000, or 5000 monomer units. In almost all cases, the polymeric material consists of a mixture of polymer molecules of different degrees of polymerization.

借助于聚合度估算的分子链长，在一个大范围内可以通过选择适宜的反应条件被改变。通常，通过大量地制备和利用聚合物，聚合度在1000～5000范围内，但在许多情况下可低于500、高于10000。这不应该把所有聚合物材料的分子量理解为由500，或1000，或5000个单体单元组成。在几乎所有的事例中，聚合物材料由不同聚合度的聚合物分子的混合物组成。

Polymerization, a chain reaction, occurs according to the same mechanism as the well-known chlorine-hydrogen reaction and the decomposition of phosegene.

聚合反应，链式反应，依照与众所周知的氯（气）-氢（气）反应和光气的分解机理进行。The initiation reaction, which is the activation process of the double bond, can be brought about by heating, irradiation, ultrasonics, or initiators. The

initiation of the chain reaction can be observed most clearly with radical or ionic initiators. These are energy-rich compounds which can add suitable unsaturated compounds (monomers) and maintain the activated radical, or ionic, state so that further monomer molecules can be added in the same manner. For the individual steps of the growth reaction one needs only a relatively small activation energy and therefore through a single activation step (the actual initiation reaction) a large number of olefin molecules are converted, as is implied by the term “chain reaction”. Because very small amounts of the initiator bring about the formation of a large amount of polymeric material (1:1000 to 1:1000), it is possible to regard polymerization from a superficial point of view as a catalytic reaction. For this reason, the initiators used in polymerization reactions are often designated as polymerization catalysts, even though, in the strictest sense, they are not true catalysts because the polymerization initiator enters into the reaction as a real partner and can be found chemically bound in the reaction product ,i.e. ,the polymer, In addition to the ionic and radical initiators there are now metal complex initiators (which can be obtained, for example, by the reaction of titanium tetrachloride or titanium trichloride with aluminum alkyls), which play an important role in polymerization reactions (Ziegler catalysts) ,The mechanism of their catalytic action is not yet completely clear.

双键活化过程的引发剂反应，可以通过热、辐射、超声波或引发剂产生。用自由基型或离子型引发剂引发链式反应可以很清楚地进行观察。这些是高能态的化合物，它们能够加成不饱和化合物（单体）并保持自由基或离子活性中心以致单体可以以同样的方式进一步加成。对于增长反应的各个步骤，每一步仅需要相当少的活化能，因此通过一步简单的活化反应（即引发反应）即可将许多烯类单体分子转化成聚合物，这正如连锁反应这个术语的内涵那样。因为少量的引发剂引发形成大量的聚合物原料（1：1000～1：10000），从表面上看聚合反应很可能是催化反应。由于这个原因，通常把聚合反应的引发剂看作是聚合反应的引发剂，但是，严格地讲它们不是真正意义上的催化剂，因为聚合反应的催化剂进入到反应内部而成为一部分，同时可以在反应产物，既聚合物的末端发现。此外离子引发剂和自由基引发剂有的是金属络合物引发剂（例如，通过四氯化钛或三氯化钛与烷基铝的反应可以得到），Z引发剂在聚合反应中起到了重要作用，它们催化活动的机理还不是十分清楚。

UNIT 3 Step-Growth Polymerization

第三单元逐步聚合

Many different chemical reactions may be used to synthesize polymeric materials by step-growth polymerization. These include esterification, amidation, the formation of urethanes, aromatic substitution, etc. Polymerization proceeds by the reactions between two different functional groups, e.g., hydroxyl and carboxyl groups, or isocyanate and hydroxyl groups.

许多不同的化学反应通过逐步聚合可用于合成聚合材料。这些反应包括酯化、酰胺化、氨

基甲酸酯、芳香族取代物的形成等。通过反应聚合反应在两种不同的官能团，如，羟基和羧基，或异氰酸酯和羟基之间。

All step-growth polymerization fall into two groups depending on the type of monomer(s) employed. The first involves two different polyfunctional monomers in which each monomer possesses only one type of functional group. A polyfunctional monomer is one with two or more functional groups per molecule. The second involves a single monomer containing both types of functional groups. The synthesis of polyamides illustrates both groups of polymerization reactions. Thus, polyamides can be obtained from the reaction of diamines with diacids

所有的逐步聚合反应根据所使用单体的类型可分为两类。第一类涉及两种不同的官能团单体，每一种单体仅具有一种官能团。一种多官能团单体每个分子有两个或多个官能团。第二类涉及含有两类官能团的单种单体。聚酰胺的合成说明了聚合反应的两个官能团。因此聚酰胺可以由二元胺和二元酸的反应或氨基酸之间的反应得到。

nH2N-R-NH2+nHO2C-R’-CO2H→

H-(-NH-R-NHCO-R’-CO-)n-OH+(2n-1)H2O (3.1)

or from the reaction of amino acids with themselves

nH2R-CO2H→ H-(-NH-R-CO-)n-OH+(n-1)H20 (3.2)

The two groups of reactions can be represented in a general manner by the equations as follows

A+B-B →–[-A-A-B-B-]-A-B→–[-A-B-]-

两种官能团之间的反应一般来说可以通过下列反应式表示

反应式略

Reaction (3.1) illustrates the former, while (3.2) is of the latter type.

反应（3.1）说明前一种形式，而反应（3.2）具有后一种形式。

图3.1 逐步聚合的示意图

未反应单体；（b）50%已反应；（c）83.3%已反应；(d) 100%已反应（虚线表示反应种类）Polyesterification, whether between diol and dibasic acid or intermolecularly between hydroxy acid molecules, is an example of a step-growth polymerization process. The esterification reaction occurs anywhere in the monomer matrix where two monomer molecules collide, and once the ester has formed, it, too, can react further by virtue of its still-reactive hydroxyl or carboxyl groups. The net effect of this is that monomer molecules are consumed rapidly without any large increase in molecular weight. Fig. 3.1 illustrates this phenomenon. Assume, for example, that each square in Fig. 3.a represents a molecule of hydroxy acid. After the initial dimmer molecules from (b), half the monomer molecules have been consumed and the average degree of polymerization (DP) of polymeric species is 2. As trimer and more dimer molecules form (c), more than 80% of the monomer molecules have reacted (d), DP is 4. But each polymer molecule that forms still has reactive end