Stoichiometry monomer-polymer reaction

Theoretical Model for Determining Monomer-Polymer Reaction Stoichiometry from Equilibrium Gel Partition... 

CH Clj were not always accurate, due to insufficient differences in RI between the solvent and copolymeric fractions (especially for polymers with substantial amount of vinytmethylsiloxane segment). Measurements in toluene gave more reliable results. However, large differences between and were observed. was found to be close to those calculated on the basis of the reaction stoichiometry and the conversion of monomers at quenching. It seems that the relationship between hydrodynamic volumes of polystyrene standards and the studied block... 

The second part deals with how polymers are prepared from monomers and the transformation of polymers into useful everyday articles. It starts with a discussion of the various polymer preparation methods with emphasis on reaction mechanisms and kinetics. The control of molecular weight through appropriate manipulation of the stoichiometry of reactants and reaction conditions is consistently emphasized. This section continues with a discussion of polymer reaction engineering. Emphasis is on the selection of the appropriate polymerization process and reactor to obtain optimal polymer properties. The section terminates with a discussion of polymer additives and reinforcements and the various unit operations in polymer processing. Here again, the primary focus is on how processing conditions affect the properties of the part produced. 

One determinant of the polymer architecture is the functionality of the monomers from which it is formed. Functionality refers to the number of bonds that a monomer can form with other monomeric molecules during the polymerization process. If the monomer is bifunctional (has a functionality of two), it will generally form a linear polymer. A molecule with a functionality of one cannot form a polymer at all. It can react with one other molecule to form a dimer, but since each of the two molecules has "used up its ability to react, it cannot grow further into a polymer. Trifunctional (or higher) monomeric units can produce either branched or cross-linked polymers, depending on the functionality of the monomer and the stoichiometry and conversion of the reaction. 

A very promising variant on this type of condensation polymerization involves the use of monomers that possess groups X and Y, which can be eliminated from the same molecule. This circumvents the need for careful control of reaction stoichiometry. Moreover, in certain cases, polymerization of monomers of this type can follow a chain-growth type of mechanism that leads to high molecular weights much more easily. Such processes (Scheme 1.1, Route C) have not yet been explored for the formation of metal-containing polymers, but are well-established for the synthesis of certain classes of polymers based on main-group elements such as polyphosphazenes (1.2) and polyoxothiazenes (1.4) [12, 16, 26]. 

With polycondensation polymerization, two monomers join to produce dimers, trimers, tetramers, and higher ohgomers and finally polymers, plus a by-product which is usually H2O. HCl, NaCl, CH3OH, and other byproducts can be formed instead of water. When a single monomer is used instead of two monomers, the reaction is self-polycondensation polymerization. Stoichiometry is monitored and controlled when two different monomers are polymerized, but stoichiometry is ensured with selfpolycondensation. Most engineering thermoplastics can be produced by polycondensation polymerization ABS, PET, PBT, polyamides (nylons), polycarbonate, PAI, LCP, TPI, PEI, PPS, PPE, PSU, and PAEK. 

For many reactions, the number of moles of products is different from the number of moles of reactants. Polymerizations are an extreme example of reactions with a large change in the number of moles. A single polymer molecule may contain as many as 10,000 monomer molecules. The stoichiometry of a chain-growth polymerization reaction can be represented as... 

The choice of solvent is not trivial and, generally, the reaction medium must be a good solvent for both monomers and polymer product. In addition, to obtain high molecular weight, water needs to be removed from the system to avoid hydrolyzing the activated substrate, since hydrolysis reduces the reaction rate and upsets the stoichiometry of the monomers.61 63... 

The stoichiometry of the redox reactions of conducting polymers (n and m in reactions 1 and 2) is quite variable. Under the most widely used conditions, polypyrroles and polythiophenes can be reversibly oxidized to a level of one hole per ca. 3 monomer units (i.e., a degree of oxidation, n, of ca. 0.3).7 However, this limit is dictated by the stability of the oxidized film under the conditions employed (Section V). With particularly dry and unreactive solvents, degrees of oxidation of 0.5 can be reversibly attained,37 and for poly-(4,4 -dimethoxybithiophene), a value of n = 1 has been reported.38 Although much fewer data are available for n-doping, it appears to involve similar stoichiometries [i.e., m in Eq. (2) is typically ca. 0.3].34,39"41 Polyanilines can in principle be reversibly p-doped to one... 

Imbalance in the stoichiometry of polycondensation reactions of AA-BB-type monomers can be overcome by changing to heterofunctional AB-type monomers. Indeed, IIMU has been subjected to bulk polycondensation using lipases as catalyst in the presence of 4 A molecular sieves. At 70 °C, CALB showed 84% monomer conversion and a low molecular weight polymer (Mn 1.1 kDa, PDI 1.9). No significant polymerization was observed with other lipases (except R cepacia lipase, 47% conversion, oligomers only) and in reference reactions with thermally deactivated CALB or in the absence of enzyme. Further optimization of the reaction conditions (60wt% CALB, II0°C, 3 days, 4 A molecular sieves) gave a polymer with Mn of 14.8 kDa (PDI 2.3) in 86% yield after precipitation [42]. 

The extension of DKR to polymer chemistry is not trivial in practice since side reactions that are relatively unimportant in DKR (dehydrogenation, hydrolysis) have a major impact on the rate of polymerization and attainable chain lengths because the stoichiometry of the reactants is an important issue. As a result, the reaction conditions and catalyst combinations used in a typical DKR process will not a priori lead to chiral polymers from racemic or achiral monomers with good molecular weight (>10kDa) and high ee (>95%). 

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