Polymers polymerization reactions

When we design commercial polymerization plants we must consider the characteristics of both the monomer and the final product. This allows us to define the optimum configuration to produce a specific polymer. Polymerization reactions can take place in homogeneous solutions or heterogeneous suspensions. For homogeneous processes, the diluted or pure monomer(s) are added directly to one another and the reaction occurs in the media created when mixing the reactants. When the reactants are added directly to one another, the process is referred to as a bulk process. With heterogeneous processes, a phase boundary exists which acts as an interface where the reaction occurs. 

The molecular weight distributions reported in Table I are seen to be quite broad for a "living polymer" polymerization reaction, although for two of the three polymerization reactions in this table tfor R2 = C2H5 and C3H7), the observed, Mj Qp, and calculated,... 

Monomers and Polymers Polymerization Reactions MiniLab 18.3 When Polymers Meet Water ChemLab Identification of Textile Polymers... 

This chapter is a comprehensive review dealing with polymerization of various OZO monomers to give a variety of polymers, polymerization reaction characteristics, and properties as well as applications of the product polymers. 

Polymerization reactions. Polymers are characterized by the distribution of molecular w eight about the mean as well as by the mean itself. The breadth of this distribution depends on whether a batch or plug-flow reactor is used on the one hand or a continuous well-mixed reactor on the other. The breadth has an important influence on the mechanical and other properties of the polymer, and this is an important factor in the choice of reactor. 

When exposed to sunlight, it is converted to a white insoluble resin, disacryl. Oxidized by air to propenoic acid small amounts of hy-droquinone will inhibit this. Bromine forms a dibromide which is converted by barium hydroxide into DL-fructose. The acrid odour of burning fats is due to traces of propenal. It is used in the production of methionine and in controlled polymerization reactions to give acrolein polymers. ... 

The successful preparation of polymers is achieved only if tire macromolecules are stable. Polymers are often prepared in solution where entropy destabilizes large molecular assemblies. Therefore, monomers have to be strongly bonded togetlier. These links are best realized by covalent bonds. Moreover, reaction kinetics favourable to polymeric materials must be fast, so tliat high-molecular-weight materials can be produced in a reasonable time. The polymerization reaction must also be fast compared to side reactions tliat often hinder or preclude tire fonnation of the desired product. 

Figure C2.1.3. Schematic dependence of tire molecular weight of a polymer as a function of tire degree of monomer conversion for different polymerization reactions.

The second category of polymerization reactions does not involve a chain reaction and is divided into two groups poly addition and poly condensation [4]. In botli reactions, tire growth of a polymer chains proceeds by reactions between molecules of all degrees of polymerization. In polycondensations a low-molecular-weight product L is eliminated, while polyadditions occur witliout elimination ... 

Our purpose in this introduction is not to trace the history of polymer chemistry beyond the sketchy version above, instead, the objective is to introduce the concept of polymer chains which is the cornerstone of all polymer chemistry. In the next few sections we shall introduce some of the categories of chains, some of the reactions that produce them, and some aspects of isomerism which multiply their possibilities. A common feature of all of the synthetic polymerization reactions is the random nature of the polymerization steps. Likewise, the twists and turns the molecule can undergo along the backbone of the chain produce shapes which are only describable as averages. As a consequence of these considerations, another important part of this chapter is an introduction to some of the statistical concepts which also play a central role in polymer chemistry. 

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. 

Although the conditions of the polymerization reaction may be chosen to optimize the formation of one specific isomer, it is typical in these systems to have at least some contribution of all possible isomers in the polymeric product, except in the case of polymers of biological origin, like natural rubber and gutta-percha. 

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-... 

Equation (5.47) is of considerable practical utility in view of the commercial importance of three-dimensional polymer networks. Some reactions of the sort we have considered are carried out on a very large scale Imagine the consequences of having a polymer preparation solidify in a large and expensive reaction vessel because the polymerization reaction went a little too far Considering this kind of application, we might actually be relieved to know that Eq. (5.47) errs in the direction of underestimating the extent of reaction at... 

In this section we examine some examples of cross-linked step-growth polymers. The systems we shall describe are thermosetting polymers of considerable industrial importance. The chemistry of these polymerization reactions is more complex than the hypothetical AB reactions of our models. We choose to describe these commercial polymers rather than model systems which might conform better to the theoretical developments of the last section both because of the importance of these materials and because the theoretical concepts provide a framework for understanding more complex systems, even if they are not quantitatively successful. 

Chain reactions do not go on forever. The fog may clear and the improved visibility ends the succession of accidents. Neutron-scavenging control rods may be inserted to shut down a nuclear reactor. The chemical reactions which terminate polymer chain reactions are also an important part of the polymerization mechanism. Killing off the reactive intermediate that keeps the chain going is the essence of these termination reactions. Some unusual polymers can be formed without this termination these are called living polymers. 

All of the reactions listed in Table 6.1 produce free radicals, so we are presented with a number of alternatives for initiating a polymerization reaction. Our next concern is in the fate of these radicals or, stated in terms of our interest in polymers, the efficiency with which these radicals initiate polymerization. Since these free radicals are relatively reactive species, there are a variety of... 

Throughout this section we have used mostly p and u to describe the distribution of molecular weights. It should be remembered that these quantities are defined in terms of various concentrations and therefore change as the reactions proceed. Accordingly, the results presented here are most simply applied at the start of the polymerization reaction when the initial concentrations of monomer and initiator can be used to evaluate p or u. The termination constants are known to decrease with the extent of conversion of monomer to polymer, and this effect also complicates the picture at high conversions. Note, also, that chain transfer has been excluded from consideration in this section, as elsewhere in the chapter. We shall consider chain transfer reactions in the next section. 

The statistical nature of polymers and polymerization reactions has been illustrated at many points throughout this volume. It continues to be important in the discussion of stereoregularity. Thus it is generally more accurate to describe a polymer as, say, predominately isotactic rather than perfectly isotactic. More quantitatively, we need to be able to describe a polymer in terms of the percentages of isotactic, syndiotactic, and atactic sequences. 

If a linear mbber is used as a feedstock for the mass process (85), the mbber becomes insoluble in the mixture of monomers and SAN polymer which is formed in the reactors, and discrete mbber particles are formed. This is referred to as phase inversion since the continuous phase shifts from mbber to SAN. Grafting of some of the SAN onto the mbber particles occurs as in the emulsion process. Typically, the mass-produced mbber particles are larger (0.5 to 5 llm) than those of emulsion-based ABS (0.1 to 1 llm) and contain much larger internal occlusions of SAN polymer. The reaction recipe can include polymerization initiators, chain-transfer agents, and other additives. Diluents are sometimes used to reduce the viscosity of the monomer and polymer mixture to faciUtate processing at high conversion. The product from the reactor system is devolatilized to remove the unreacted monomers and is then pelletized. Equipment used for devolatilization includes single- and twin-screw extmders, and flash and thin film evaporators. Unreacted monomers are recovered for recycle to the reactors to improve the process yield. 

The Fischer-Tropsch process can be considered as a one-carbon polymerization reaction of a monomer derived from CO. The polymerization affords a distribution of polymer molecular weights that foUows the Anderson-Shulz-Flory model. The distribution is described by a linear relationship between the logarithm of product yield vs carbon number. The objective of much of the development work on the FT synthesis has been to circumvent the theoretical distribution so as to increase the yields of gasoline range hydrocarbons. 

THPC—Amide Process. The THPC—amide process is the first practical process based on THPC. It consists of a combination of THPC, TMM, and urea. In this process, there is the potential of polymer formation by THPC, melamine, and urea. There may also be some limited cross-linking between cellulose and the TMM system. The formulation also includes triethanolamine [102-71-6J, an acid scavenger, which slows polymerization at room temperature. Urea and triethanolamine react with the hydrochloric acid produced in the polymerization reaction, thus preventing acid damage to the fabric. This finish with suitable add-on passes the standard vertical flame test after repeated laundering (80). 

Polyamines can also be made by reaction of ethylene dichloride with amines (18). Products of this type are sometimes formed as by-products in the manufacture of amines. A third type of polyamine is polyethyleneimine [9002-98-6] which can be made by several routes the most frequently used method is the polymeriza tion of azitidine [151 -56 ] (18,26). The process can be adjusted to vary the amount of branching (see Imines, cyclic). Polyamines are considerably lower in molecular weight compared to acrylamide polymers, and therefore their solution viscosities are much lower. They are sold commercially as viscous solutions containing 1—20% polymer, and also any by-product salts from the polymerization reaction. The charge on polyamines depends on the pH of the medium. They can be quaternized to make their charge independent of pH (18). 

Synthetic Fiber and Plastics Industries. In the synthetic fibers and plastics industries, the substrate itself serves as the solvent, and the whitener is not appHed from solutions as in textiles. Table 6 Hsts the types of FWAs used in the synthetic fibers and plastic industries. In the case of synthetic fibers, such as polyamide and polyester produced by the melt-spinning process, FWAs can be added at the start or during the course of polymerization or polycondensation. However, FWAs can also be powdered onto the polymer chips prior to spinning. The above types of appHcation place severe thermal and chemical demands on FWAs. They must not interfere with the polymerization reaction and must remain stable under spinning conditions. 

Interfacial Polymerization. Many types of polymerization reactions can be made to occur at interfaces or produce polymers that concentrate at interfaces thereby producing microcapsules. Accordingly, this approach to encapsulation has steadily developed into a versatile family of encapsulation processes. Figure 4 schematically illustrates five types of encapsulation processes that utilize these types of reactions. 

Polyethylene (PE) is a genetic name for a large family of semicrystalline polymers used mostiy as commodity plastics. PE resins are linear polymers with ethylene molecules as the main building block they are produced either in radical polymerization reactions at high pressures or in catalytic polymerization reactions. Most PE molecules contain branches in thek chains. In very general terms, PE stmcture can be represented by the following formula ... 

Dicyclopentadiene is also polymerized with tungsten-based catalysts. Because the polymerization reaction produces heavily cross-Unked resins, the polymers are manufactured in a reaction injection mol ding (RIM) process, in which all catalyst components and resin modifiers are slurried in two batches of the monomer. The first batch contains the catalyst (a mixture of WCl and WOCl, nonylphenol, acetylacetone, additives, and fillers the second batch contains the co-catalyst (a combination of an alkyl aluminum compound and a Lewis base such as ether), antioxidants, and elastomeric fillers (qv) for better moldabihty (50). Mixing two Uquids in a mold results in a rapid polymerization reaction. Its rate is controlled by the ratio between the co-catalyst and the Lewis base. Depending on the catalyst composition, solidification time of the reaction mixture can vary from two seconds to an hour. Similar catalyst systems are used for polymerization of norbomene and for norbomene copolymerization with ethyhdenenorbomene. 

The reaction rate of fumarate polyester polymers with styrene is 20 times that of similar maleate polymers. Commercial phthaHc and isophthaHc resins usually have fumarate levels in excess of 95% and demonstrate full hardness and property development when catalyzed and cured. The addition polymerization reaction between the fumarate polyester polymer and styrene monomer is initiated by free-radical catalysts, commercially usually benzoyl peroxide (BPO) and methyl ethyl ketone peroxide (MEKP), which can be dissociated by heat or redox metal activators into peroxy and hydroperoxy free radicals. 

The neat resin preparation for PPS is quite compHcated, despite the fact that the overall polymerization reaction appears to be simple. Several commercial PPS polymerization processes that feature some steps in common have been described (1,2). At least three different mechanisms have been pubUshed in an attempt to describe the basic reaction of a sodium sulfide equivalent and -dichlorobenzene these are S Ar (13,16,19), radical cation (20,21), and Buimett s (22) Sj l radical anion (23—25) mechanisms. The benzyne mechanism was ruled out (16) based on the observation that the para-substitution pattern of the monomer, -dichlorobenzene, is retained in the repeating unit of the polymer. Demonstration that the step-growth polymerization of sodium sulfide and /)-dichlorohenzene proceeds via the S Ar mechanism is fairly recent (1991) (26). Eurther complexity in the polymerization is the incorporation of comonomers that alter the polymer stmcture, thereby modifying the properties of the polymer. Additionally, post-polymerization treatments can be utilized, which modify the properties of the polymer. Preparation of the neat resin is an area of significant latitude and extreme importance for the end user. 

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