Chain polymerization combination

ESI mass spectrometry ive mass spectrometry ESR spectroscopy set EPR spectroscopy ethyl acetate, chain transfer to 295 ethyl acrylate (EA) polymerizalion, transfer constants, to macromonomers 307 ethyl methacrylate (EMA) polymerization combination v.v disproportionation 255, 262 kinetic parameters 219 tacticity, solvent effects 428 thermodynamics 215 ethyl radicals... 

Porous organic polymers (Figure 10) are potential electrochromatographic stationary phases for the analysis of pharmaceuticals. The polymer network is generally formed inside the capillary by a stepwise chain polymerization reaction. Polymerization reaction mixtures usually consist of a combination of monomers and cross-linker, initiator, and a porogenic mixture of solvents. 

Hyperbranched polymers can also be synthesized by chain polymerization, ring-opening polymerization, and combinations of ring-opening and step polymerization [Kim, 1998 Voit, 2000] (Secs. 3-6e, 3-15b-4, 3-15b-5, 3-15c, 5-4c). 

Consider the activation energy for various radical chain polymerizations. For a polymerization initiated by the thermal decomposition of an initiator, the polymerization rate depends on the ratio of three rate constants kp (kj/k,) 2 in accordance with Eq. 3-32. The temperature dependence of this ratio, obtained by combining three separate Arrhenius-type equations, is given by... 

Peroxide crosslinking of the copolymer is more efficient than that of the homopolymer (Table 9-1). The process becomes a chain reaction (but with short kinetic chain length) involving polymerization of the pendant vinyl groups on the polysiloxane chains in combination with coupling of polymeric radicals. The crosslinking of EPDM rubbers is similarly more efficient when compared to EPM rubbers since the former contain double bonds in the polymer chain. 

The addition of the anion takes place at the unsubstituted carbon atom, which, in this case, carries a partial positive charge. Since the growing chain end is a genuine anion, chain termination can occur by addition of a reactive cation. As in cationic polymerization, combination of two growing ends is not possible. Chain transfer with electrophiles can also occur. 

In the 1960s, anionic polymerized solutron SBR (SSBR) began to challenge emulsion SBR in the automotive tire market. Organolithium compounds allow control of the butadiene microstructure, not possible with ESBR. Because this type of chain polymerization takes place without a termination step, an easy synthesis of block polymers is available, whereby glassy (polystyrene) and rubbery (polybutadicnc) segments can be combined in the same molecule. These thermoplastic elastomers (TPE) have found use ill nontire applications. 

However, even the complete understanding of these areas will not suffice to reap the full benefits embedded in the macromolecular nature of polymeric materials, which are inherent in the naturally occurring and synthetic polymeric building blocks. For that, a priori quantitative prediction of product properties, made of yet nonexistent chains or combinations of chains of different monomeric building blocks from basic principles, requiring information of only the macromolecular structure and processing conditions, is needed. 

Condensation Polymerization. As shown previously, condensation polymerization is characterized by polymer chains that combine both with each other and with monomer units to give larger chains capable of further reaction (Table VI). Like stepwise addition without termination,... 

In a step-growth polymerization, any two monomers having the correct functionality can react with each other, or two polymer chains can combine. Most step-growth polymers are condensation polymers, bonded by some kind of condensation (bond formation with loss of a small molecule) between the monomers or the polymer segments. The most common condensations involve the formation of amides and esters. Dacron polyester is an example of a step-growth condensation polymer. 

As in so many things in this field, if you want to work through the arguments yourself, you cannot do better than go to Flory— see Principles of Polymer Chemistry, Chapter EX. Stockmayer s equation illustrates the point we wish to make with dazzling simplicity as f the number of branches, increases, the polydispersity decreases. Thus for values of/equal to 4, 5 and 10, the polydispersity values are 1.25, 1.20 and 1.10, respectively. Note also that for / = 2, where two independent chains are combined to form one linear molecule (Figure 5-28), the polydispersity is predicted to be 1.5. Incidentally, an analogous situation occurs in free radical polymerization when chain termination is exclusively by combination. 

Steric stabilization is another well-established method of stabilizing colloidal suspensions of submicron to micron size [23]. The particles are coated with a layer of adsorbed or grafted polymer chains that provides a steric repulsion of entropie origin and helps disperse the particles by counterbalancing van der Waals attraction (Fig. la). The polymeric nature of the adsorbed or grafted layer softens the interparticle interactions and makes the particles intrinsically deformable. Many polymer chain/particle combinations have been synthesized and studied, and are described in the literature. Several popular colloidal systems consist of silica particles covered with various polymers such as polydimethylsiloxane [24], stearyl alcohol [25], alkyl chains [26], and polyethylene oxide [27]. Polymethylmethacrylate and polystyrene particles grafted with polymer chains have also been used extensively. For a review on the impressive literature on the subject we refer the interested reader to Vlassopoulos and Fytas [2]. 

Chain polymerization involves three processes chain initiation, chain propagation, and chain termination. (A fourth process, chain transfer, may also be involved, but it may be regchain termination and chain initiation.) Chain initiation occurs by an attack on... 

One of the interesting things about the redox polymers is their use in the creation of the molecular electronic devices.3-5 Redox polymer films on electrodes have been fabricated using chemical modification, electrochemical polymerization, polymer coating, and so on.88 Recently, stepwise complexation methods have been employed to fabricate multiple complex layers.89,90,91 In this section, the stepwise preparation of bis(tpy)metal polymer chains by combining terpyridine (tpy) ligand self-assembled monolayer (SAM) formation and metal-tpy coordination reactions is described as an example. This method realized the formation of a desired number of polymer units and a desired sequence of Co-Fe heterometal structures in the polymer chain.92... 

Timothy E. Long is a professor of chemistry at Virginia Polytechnic Institute and State University. His efforts are focused on the synthesis and characterization of novel macromolecules using unique combinations of step-growth and chain polymerization processes. He received a B.S. from St. Bonaventure University and a Ph.D. from Virginia Polytechnic Institute and State University. 

Figure 13.3 Overview showing the use of bifunctional initiators for block-copolymer synthesis. Two examples using either reversible addition fragmentation chain transfer polymerization or atom transfer radical polymerization combined with eROP are shown.

---