Polymerization, cationic step growth

Anionic and Cationic Polymerizations o Radical Polymerization Advances o Coordination Polymerizations 0 Step-Growth Polymerization Advances 0 Synthesis of Tactic Polymers o Stereoblock Copolymers o Dispersion Polymerizations o Cellulosic Graft Copolymers o Diels-Alder Polymer Forming Reactions o A New Path To Phenolic Resins o Nitrogen Heterocycle Polymerizations o Optically Active Polymers o Poly (Phenylene Sulfide) o Poly (Aryl Ethers) o (Poly (Aryl Ether Sulfones) o Epoxy and Isocyanate Resin Replacement o Azlactone Functionalized Oligomers o Epoxy Resin-Isocyanate Reactions o Chelating Polymers o Oxazoline Functionalized Polymers o Poly (Alkyl Methacrylates) o Macromers... 

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. 

Synthetic polymers can be classified as either chain-growth polymen or step-growth polymers. Chain-growth polymers are prepared by chain-reaction polymerization of vinyl monomers in the presence of a radical, an anion, or a cation initiator. Radical polymerization is sometimes used, but alkenes such as 2-methylpropene that have electron-donating substituents on the double bond polymerize easily by a cationic route through carbocation intermediates. Similarly, monomers such as methyl -cyanoacrylate that have electron-withdrawing substituents on the double bond polymerize by an anionic, conjugate addition pathway. 

The degree of polymerization depends on the duration of the process. After 7 min, the molecular mass is equal to 9400 (the polydispersity index is 5.30). When the reaction is carried out for 15 min, the molecular mass of the polymer increases to 37,000 and the polydispersity index reaches 7.31 (Bauld et al. 1996). Depending on whether cation-radical centers arise at the expense of intramolecular electron transfer or in a stepwise intermolecular lengthening, polymerization can occur, respectively, through a chain or a step-growth process (Bauld and Roh 2002). In the reaction depicted in Scheme 7.17, both chain and step-growth propagations are involved. 

Hence, cation-radical copolymerization leads to the formation of a polymer having a lower molecular weight and polydispersity index than the polymer got by cation-radical polymerization— homocyclobutanation. Nevertheless, copolymerization occnrs nnder very mild conditions and is regio-and stereospecihc (Bauld et al. 1998a). This reaction appears to occnr by a step-growth mechanism, rather than the more efficient cation-radical chain mechanism proposed for poly(cyclobutanation). As the authors concluded, the apparent suppression of the chain mechanism is viewed as an inherent problem with the copolymerization format of cation-radical Diels-Alder polymerization. ... 

Many researchers have investigated the use of amines and alcohols as initiators for the ROP of lactones. As a rule, amines and alcohols are not nucleophilic enough to be efficient initiators, and it is then mandatory to use catalysts to perform the polymerization successfully. Nevertheless, highly reactive p-lactones exhibit a particular behavior because their polymerization can be initiated by nucleophilic amines in the absence of any catalyst. As far as tertiary amines are concerned, the initiation step implies the formation of a zwitterion made up of an ammonium cation and a carboxylate anion, as shown in Fig. 20. Authors coined the name zwitterionic polymerization for this process [80]. Nevertheless, this polymerization is not really new because the mechanism is mainly anionic. Interestingly, Rticheldorf and coworkers did not exclude the possibility that, at least at some stage of the polymerization, chain extension takes place by step-growth polycondensation [81]. 

Cationically catalyzed polymerizations28,72 have not received as much attention as the anionic variety. Typical cationic (acidic) catalysts in this case are Lewis acids. Yields and proportions of the various species are generally very similar to those obtained in anionic polymerizations, although the mechanism is very different. The reaction is thought to proceed through a tertiary oxonium ion formed by addition of a proton to one of the O atoms of the cyclic siloxane. Part of the mechanism may involve step growth, as well as the expected chain growth. 

In addition to post-functionalizing polymers by bonding the macrocycle to the preformed polymer backbone, macrocycles can be incorporated into polymer matrices by direct polymerization of the macrocycle, either by a step-growth mechanism or a chain-growth mechanism. [46] Polymeric crown ether stationary phases were pioneered by Blasius et al. [34, 59-62] These resins were used to separate both cations (including protonated amines) with a common anion, and anions with a common cation in high... 

A macromonomer is a macromolecule with a reactive end group that can be homopolymerized or copolymerized with a small monomer by cationic, anionic, free-radical, or coordination polymerization (macromonomers for step-growth polymerization will not be considered here). The resulting species may be a star-like polymer (homopolymerization of the macromonomer), a comblike polymer (copolymerization with the same monomer), or a graft polymer (copolymerization with a different monomer) in which the branches are the macromonomer chains. 

Use mechanisms to show how monomers polymerize under acidic, basic, or free-radical conditions. For chain-growth polymerization, determine whether the reactive end is more stable as a cation (acidic conditions), anion (basic conditions), or free radical (radical initiator). For step-growth polymerization, consider the mechanism of the condensation. 

Formulate the mechanisms of radical, cationic, anionic, and step-growth polymerizations. 

Chain growth differs from step growth in that it involves initiation and usually also termination reactions in addition to actual growth. This makes its kinetic behavior similar to that of chain reactions (see Chapter 9). However, the chain carriers in chain-growth polymerization need not be free radicals, as they are in ordinary chain reactions. Instead, they could be anions, cations, or metal-complex adducts. While the general structure of kinetics is similar in all types of chain-growth polymerizations, the details differ depending on the nature of the chain carriers. 

Kinetic aspects of step-growth copolymerization have been examined in Section 10.2.2. The principal features of chain-growth copolymerization are very different, but are alike for all types of chain growth, that is, for free-radical, anionic, cationic, and coordination polymerization. 

Both the monomer and polymer are soluble in the solvent in these reactions. Fairly high polymer concentrations can be obtained by judicious choice of solvent. Solution processes are used in the production of c(5-polybutadiene with butyl lithium catalyst in hexane solvent (Section 9.2.7). The cationic polymerization of isobutene in methyl chloride (Section 9.4.4) is initiated as a homogeneous reaction, but the polymer precipitates as it is formed. Diluents are necessary in these reactions to control the ionic polymerizations. Their use is avoided where possible in free-radical chain growth or in step-growth polymerizations because of the added costs involved in handling and recovering the solvents. 

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