Polymerization reactions classes

In the last section we examined some of the categories into which polymers can be classified. Various aspects of molecular structure were used as the basis for classification in that section. Next we shall consider the chemical reactions that produce the molecules as a basis for classification. The objective of this discussion is simply to provide some orientation and to introduce some typical polymers. For this purpose a number of polymers may be classified as either addition or condensation polymers. Each of these classes of polymers are discussed in detail in Part II of this book, specifically Chaps. 5 and 6 for condensation and addition, respectively. Even though these categories are based on the reactions which produce the polymers, it should not be inferred that only two types of polymerization reactions exist. We have to start somewhere, and these two important categories are the usual place to begin. 

In the next group of chapters we shall discuss condensation or step-growth polymers and polymerizations in Chap. 5, addition or chain-growth polymers and polymerizations in Chap. 6, and copolymers and stereoregular polymers in Chap. 7. It should not be inferred from this that these are the only classes of polymers and polymerization reactions. Topics such as ring-opening polymeri-... 

Polymerization Reactions. Polymerization addition reactions are commercially the most important class of reactions for the propylene molecule and are covered in detail elsewhere (see Olefin polymers, polypropylene). Many types of gas- or liquid-phase catalysts are used for this purpose. Most recently, metallocene catalysts have been commercially employed. These latter catalysts requite higher levels of propylene purity. 

We have reviewed experiments on two classes of systems, namely small metal particles and atoms on oxide surfaces, and Ziegler-Natta model catalysts. We have shown that metal carbonyls prepared in situ by reaction of deposited metal atoms with CO from the gas phase are suitable probes for the environment of the adsorbed metal atoms and thus for the properties of the nucleation site. In addition, examples of the distinct chemical and physical properties of low coordinated metal atoms as compared to regular metal adsorption sites were demonstrated. For the Ziegler-Natta model catalysts it was demonstrated how combination of different surface science methods can help to gain insight into a variety of microscopic properties of surface sites involved in the polymerization reaction. 

Our interest in such compounds stems mainly from the possibility that they might be useful precursors to new classes of phosphorus-containing polymers or cyclic oligomers. Functional linkages such as E = NSiMe3 or CR SiMe3 could serve as sites for condensation-polymerization reactions, leading to novel cyclic or polymeric sys terns, ... 

Polymer class names relevant only to the main chain are specified in the name names of side-chain functional groups may also be included after a hyphen if they are formed during the polymerization reaction. 

One recent development in Ziegler Natta catalysts was in producing catalyst particles that expanded as the polymerization reaction occurred. In this polymer the catalyst remains dispersed throughout the polymer, retaining its activity. This led to the development of fluidized bed processes to make polyethylene and polypropylene in which a sphere of polymer formed around each initial catalyst particle, and the polymer remained sohd as the reaction proceeded, rather than requiring a liquid solution. A major class of these catalysts and fluidized bed reactor was developed by Union Carbide and by Shell Oil and called the Unipol process. In this process a very active solid catalyst is introduced into the reactor, and reaction occurs on the catalyst particles, which expand to maintain active sites on the growing polymer sphere. 

Lipases belong to the subclass of serine hydrolases, and their structure and reaction mechanism are well understood. Their common a/p-hydrolase enzyme fold is characterized by an a-helix that is connected with a sharp turn, referred to as the nucleophilic elbow, to the middle of a P-sheet array. All lipases possess an identical catalytic triad consisting of an Asp or Gin residue, a His and a nucleophilic Ser [14]. The latter residue is located at the nucleophilic elbow and is found in the middle of the highly conserved Gly—AAl—Ser—AA2—Gly sequence in which amino acids AAl and AA2 can vary. The His residue is spatially located at one side of the Ser residue, whereas at the opposite side of the Ser a negative charge can be stabilized in the so-called oxyanion hole by a series of hydrogen bond interactions. The catalytic mechanism of the class of a/P-hydrolases is briefly discussed below using CALB as a typical example, since this is the most commonly applied lipase in polymerization reactions [15]. 

Although the biochemistry of the synthesis of glycosyl-nucleotides in higher plants is well advanced, the subsequent polymerization reactions, involving their glycosyl groups, to yield the various classes of cell-wall polysaccharides is not. The enzymes catalyzing these processes have not yet been fully characterized, and the involvement of membrane systems, and the mechanism of assembly of the wall itself, are ill-understood. 

Since the aldehyde complex has a novel type of structure and clearly plays an important role in the polymerization reaction of an aldehyde, the chemical behavior of this class of compound was examined. 

High molecular weight, linear, aromatic ether polymers have recently been prepared by a variety of methods. This review will cover the principal methods that have been used to prepare this new class of high molecular weight polymers. The chemistry of the polymerization reactions involved as well as the properties of the resulting polymers will be described. 

Microbial polysaccharides constitute a specific class of biopolymers. These biopolymers are formed during the growth of the living organisms, and are thus, called natural polymers. Their synthesis usually involves enzymatic catalysis and an increase in the chain through polymerization reactions of the monomers, typically inside the cells, mediated by complete metabolic processes (3,4). 

During the early 1960 s a new class of chemicals containing one or more double bonds was used to treat wood vinyl type monomers that could be polymerized into the solid polymer by means of free radicals (2). This vinyl polymerization was an improvement over the condensation polymerization reaction because the free radical catalyst was neither acidic nor basic, nor does the reaction leave behind a reaction product that must be removed from the final composite, such as water. The acid and base catalysts used with the other treatments degrade the cellulose chain and cause brittleness of the composite. Vinyl polymers have a large range of properties from soft rubber to hard brittle solids depending upon the groups attached to the carbon-carbon backbone. 

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