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高分子专业英语选讲课文翻译资料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 (544 000)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, 1986.6UNIT 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 (200020000 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200020000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10005000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（1：10001：10000），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-CO2HH-(-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 groups; hence the polymerization reaction will continue in a stepwise fashion, with each esterification of monomers. Thus, molecular weight increases slowly even at high levels of monomer conversion, and it will continue to increase until the viscosity build-up makes it mechanically too difficult to remove water of esterification or for reactive end groups to find each other. 聚酯化，是否在二元酸和二元醇或羟基酸分子间进行，是逐步聚合反应过程的一个例子。酯化反应出现在单体本体中两个单体分子相碰撞的位置，且酯一旦形成，依靠酯上仍有活性的羟基或羧基还可以进一步进行反应。酯化的结果是单体分子很快地被消耗掉，而分子量却没有多少增加。图3.1说明了这个现象。例如，假定图3.1中的每一个方格代表一个羟基酸分子。（b）中的二聚体分子，消耗二分之一的单体分子聚合物种类的聚合度（DP）是2。（c）中当三聚体和更多的二聚体形成，大于80%的单体分子已反应，但DP仅仅还是2.5。（d）中当所有的单体反应完，DP是4。但形成的每一种聚合物分子还有反应活性的端基；因此，聚合反应将以逐步的方式继续进行，其每一步酯化反应的反应速率和反应机理均与初始单体的酯化作用相同。因此，分子量缓慢增加直至高水平的单体转化率，而且分子量将继续增加直到粘度的增加使其难以除去酯化反应的水或难以找到相互反应的端基。It can also be shown that in the A-A+B-B type of polymerization, an exact stoichiometric balance is necessary to achieve high molecular weights. If some monofunctional impurity is present, its reaction will limit the molecular weight by rendering a chain end inactive. Similarly, high-purity monomers are necessary in the A-B type of polycondensation and it follows that high-yield reactions are the only practical ones for polymer formation, since side reactions will upset the stoichiometric balance.在A-A+B-B的聚合反应中也可以看到，精确的当量平衡是获得高分子量所必需的。假如存在一些但官能团杂质，由于链的端基失活，反应将使分子量减少。同样，在A-B类的缩聚反应中高纯度的单体是必要的，而且可以归结高收率的反应仅是形成聚合物的实际反应，因为副反应会破坏当量平衡。-Stevens M P. Polymer Chemistry. London: Addison-Wesley Publishing Company, 1975. 13UNIT 4 Ionic Polymerization第四单元 离子聚合反应Ionic polymerization, similar to radial polymerization, also has the mechanism of a chain reaction. The kinetics of ionic polymerization are, however, considerably different from that of radical polymerization.离子聚合反应，与自由基聚合反应相似，也有链反应的机理。但是，离子聚合的动力学明显地不同于自由基聚合反应。(1) The initiation reaction of ionic polymerization needs only a small activation energy. Therefore, the rate of polymerization depends only slightly on the temperature. Ionic polymerizations occur in many cases with explosive violence even at temperature. below 50(for example, the anionic polymerization of styrene at 70 in tetrahydrofuran, or the cationic polymerization of isobutylene at 100 in liquid ethylene ).(1)离子聚合的引发反应仅需要很小的活化能。因此，聚合反应的速率仅对温度有较少的依赖性。在许多情况下离子聚合猛烈地发生甚至低于50（例如，苯乙烯的阴离子聚合反应在-70在四氢呋喃中，或异丁烯的阳离子聚合在-100在液态乙烯中）。(2) With ionic polymerization there is no compulsory chain termination through recombination, because the growing chains can not react with each other. Chain termination takes place only through impurities, or through the addition of certain compounds such as water, alcohols, acids, amines, or oxygen, and in general through compounds which can react with polymerization ions under the formation of neutral compounds or inactive ionic species. If the initiators are only partly dissociated, the initiation reaction is an equilibrium reaction, where reaction in one direction gives rise to chain initiation and in the other direction to chain termination.（2）对于离子聚合来说，不存在通过再结合反应而进行的强迫链终止，因为生长链之间不能发生链终止。链终止反应仅仅通过杂质而发生，或者说通过和某些像水、醇、酸、胺或氧这样的化合物进行加成而发生，且一般来说（链终止反应）可通过这样的化合物来进行，这种化合物在中性聚合物或没有聚合活性的离子型聚合物生成的过程中可以和活性聚合物离子进行反应。如果引发剂仅仅部分地离解，引发反应即为一个平衡反应，在出现平衡反应的场合，在一个方向上进行链引发反应，而在另一个方向上则发生链终止反应。In general ionic polymerization polymerization can be initiated through acidic or basic compounds. For cationic polymerization, complexes of BF3, AlCl3, TiCl4, and SnCl4 with water, or alcohols, or tertiary oxonium salts have shown themselves to be particularly active. The positive ions are the ones that cause chain initiation. For example:通常离子聚合反应能通过酸性或碱性化合物被引发。对于阳离子聚合反应来说，BF3,AlCl3,TiCl4和SnCl4与水、或乙醇，或叔烊盐的络合物提供了部分活性。正离子是产生链引发的化合物。例如：(反应略)三乙基硼氟酸烊 However, also with HCl, H2SO4, and KHSO4, one can initiate cationic polymerization. Initiators for anionic polymerization are alkali metals and their organic compounds, such as phenyllithium, butyllithium, phenyl sodium, and triphenylmethyl potassium, which are more or less strongly dissociated in different solvents. To this group belong also the so called Alfin catalysts, which are a mixture of sodium isopropylate, allyl sodium, and sodium chloride.然而，BF3也可以与HCl、H2SO4和KHSO4引发阳离子聚合反应。阴离子聚合反应的引发剂是碱金属和它们的有机金属化合物，例如苯基锂、丁基锂和三苯甲基锂，它们在不同的溶剂中或多或少地强烈分解。所谓的Alfin催化剂就是属于这一类，这类催化剂是异丙醇钠、烯丙基钠和氯化钠的混合物。With BF3 (and isobutylene as the monomer), it was demonstrated that the polymerization is possible only in the presence of traces of traces of water or alcohol. If one eliminates the trace of water, BF3 alone does not give rise to polymerization. Water or alcohols are necessary in order to allow the formation of the BF3-complex and the initiator cation according to the above reactions. However, one should not describe the water or the alcohol as a “cocatalyst”.BF3为引发剂（异丁烯为单体），证明仅在痕量水或乙醇的存在下聚合反应是可以进行的。如果消除痕量的水，单纯的BF3不会引发聚合反应。按照上述反应为了能形成BF3-络合物和引发剂离子水或乙醇是必需的。但是不应将水或乙醇描述成“助催化剂”。Just as by radical polymerization, one can also prepare copolymers by ionic polymerization, for example, anionic copolymers of styrene and butadiene, or cationic copolymers of isobutylene and styrene, or isobutylene and viny ethers, etc. As has been described in detail with radical polymerization, one can characterize each monomer pair by so-called reactivity ratios r1 and r2. The actual values of these two parameters are, however, different from those used for radical copolymerization.正与自由基聚合反应一样，通过离子聚合反应也能制备共聚物，例如，苯乙烯-丁二烯阴离子共聚物，或异丁烯-苯乙烯阳离子共聚物，或异丁烯-乙烯基醚共聚物，等等。正如对自由基型聚合已经详细描述过那样，人们可以用所谓的竞聚率r1和r2来表征每单体对。然而，这两个参数的实际意义不同于那些用于自由基共聚合反应的参数。-Vollmert B. Polymer Chemistry. Berlin: Sping-Verlag, 1973.163PART B 聚合反应工程UNIT 11 Reactor types第十一单元 反应器类型Reactors may be categorized in a variety of ways, each appropriate to a particular perspective. For example, Henglein (1969) chooses a breakdown based on the source of energy used to initiate the reaction (i.e., thermal, electrochemical, photochemical, nuclear). More common breakdowns are according to the types of vessels and flows that exist.反应器可以用许多方法分类，各自适用于特定的目的。例如，Henglein（1969）基于用于产生反应的能量来源，即，热量，电化学，光化学，原子核，选择了一种细目分类。更多普通的细目分类是按照所存在的容器和流量的类型。Batch Reactors1. 间歇反应器The batch reactor (BR) is the almost universal choice in the chemists laboratory where most chemical processes originate. The reason is the simplicity and versatility of the batch reactor, whether it be a test tube, a three-neck flask, an autoclave, or a cell in a spectroscopic instrument. Regardless of the rate of the reaction, these are clearly low production rate devices. As scale up is desired, the most straightforward approach is to move to a larger batch reactor such as a large vat or tank.间歇反应器在化学实验室几乎是一般的选择，大多数的化学过程在那里产生。间歇反应器的原理具简单性和通用性，不管它是一支试管，一个三颈瓶，一个高压釜，还是一个光谱仪器的比色皿。不管反应比例，很清楚这些是低产率设备。当要求放大反应器时，大多直截了当的途径是移至一个较大的间歇反应器如一个较大的大桶或罐。Commercial batch reactors can be huge, 100 000 gal or more. The cycle time, often a day or more, typically becomes longer as reactor volume increases in order to achieve a substantial production rate with an inherently slow reaction. Fabrication, shipping, or other facto
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