Star polymerization

The details of the anionic polymerization of nylon 6 have been extensively reviewed (1-8) and will only be discussed briefly as they affect the star-polymerization of nylon 6. Nylon 6 is polymerized anionically in a two-step process (Figure 1). The first step, creation of the activated species 3, is the slow step. The e-caprolactam monomer reacts in the presence of a strong base (such as sodium hydride) to form the caprolactam anion 2. This anion reacts with more caprolactam monomer to form 3. The reaction of this activated species with lactam anions occurs rapidly to form the nylon 6 polymer 4. 

TABLE 2. Physical properties of polymers in the star polymerization of methyl methacrylate using the trifunctional photoiniferter, (I). 

A variety of mnltifnnctional CTAs have been used for the preparation of star (co)polymers via RAFT polymerization, the core (or hub) of the star being introduced via functionalization of either the R substiment (R-group approach or R approach) or the Z substituent (Z-group approach or Z approach). Typical examples of fimctional CTAs used for the production of star (co)polymers in R- and Z-group approaches are shown in Fig. 11.40. The difference between the two approaches is shown schematically in Fig. 11.41, while a mechanism for RAFT star polymerization proposed byBameretal. (2007) is presented in Fig. 11.42. 

Figure 11.42 RAFT star polymerization mechanisms (pre-equilibrium and main equilibrium stages) R-vs. Z-group approach (shown for one arm only). Formation mechanisms of chain radicals P and are same for R- and Z-group approaches and same as shown in Fig.11.36. (Adapted from Earner et al., 2007.)...

Problem 11.24 Besides choosing the Z-approach, what are the key factors that determine the success of the RAFT star polymerization process to achieve large proportion of well-de ned star polymers of controlled stmctures . 

Syrett JA, Haddleton DM, Whittaker MR, Davis TP, Boyer C (2011) Fimctional, star polymeric molecular carriers, built from biodegradable microgel/nanogel cores. Chem Commun 47 1449-1451... 

The conditions used for the synthesis of star polymerization of methyl methacrylate has been extended to lauryl methacrylate (LMA). However, the linear living poly(LMA) chain end did not undergo star pol)mierization with EGDMA. However, when a second dose of catalyst was introduced after the complete homopolymerization of LMA, prior to addition of EGDMA, star formation was found to occur. Poly(LMA) stars with a polydispersity of 1.9 and possessing up to ten arms could be prepared [31]. 

The anionic polymerization of methacrylates using a silyl ketene acetal initiator has been termed group-transfer polymerization (GTP). First reported by Du Pont researchers in 1983 (100), group-transfer polymerization allows the control of methacrylate molecular stmcture typical of living polymers, but can be conveniendy mn at room temperature and above. The use of GTP to prepare block polymers, comb-graft polymers, loop polymers, star polymers, and functional polymers has been reported (100,101). 

Block copolymer chemistry and architecture is well described in polymer textbooks and monographs [40]. The block copolymers of PSA interest consist of anionically polymerized styrene-isoprene or styrene-butadiene diblocks usually terminating with a second styrene block to form an SIS or SBS triblock, or terminating at a central nucleus to form a radial or star polymer (SI) . Representative structures are shown in Fig. 5. For most PSA formulations the softer SIS is preferred over SBS. In many respects, SIS may be treated as a thermoplastic, thermoprocessible natural rubber with a somewhat higher modulus due to filler effect of the polystyrene fraction. Two longer reviews [41,42] of styrenic block copolymer PSAs have been published. 

As discussed in Section 7.3, conventional free radical polymerization is a widely used technique that is relatively easy to employ. However, it does have its limitations. It is often difficult to obtain predetermined polymer architectures with precise and narrow molecular weight distributions. Transition metal-mediated living radical polymerization is a recently developed method that has been developed to overcome these limitations [53, 54]. It permits the synthesis of polymers with varied architectures (for example, blocks, stars, and combs) and with predetermined end groups (e.g., rotaxanes, biomolecules, and dyes). 

Platinum-cobalt alloy, enthalpy of formation, 144 Polarizability, of carbon, 75 of hydrogen molecule, 65, 75 and ionization potential data, 70 Polyamide, 181 Poly butadiene, 170, 181 Polydispersed systems, 183 Polyfunctional polymer, 178 Polymerization, of butadiene, 163 of solid acetaldehyde, 163 of vinyl monomers, 154 Polymers, star-shaped, 183 Polymethyl methacrylate, 180 Polystyrene, 172 Polystyril carbanions, 154 Potential barriers of internal rotation, 368, 374... 

There are additional factors that may reduce functionality which are specific to the various polymerization processes and the particular chemistries used for end group transformation. These are mentioned in the following sections. This section also details methods for removing dormant chain ends from polymers formed by NMP, ATRP and RAFT. This is sometimes necessary since the dormant chain-end often constitutes a weak link that can lead to impaired thermal or photochemical stability (Sections 8.2.1 and 8.2.2). Block copolymers, which may be considered as a form of end-functional polymer, and the use of end-functional polymers in the synthesis of block copolymers are considered in Section 9.8. The use of end functional polymers in forming star and graft polymers is dealt with in Sections 9.9.2 and 9.10.3 respectively. 

The generic features of these approaches are known from experience in anionic polymerization. However, radical polymerization brings some issues and some advantages. Combinations of strategies (a-d) are also known. Following star formation and with appropriate experimental design to ensure dormant chain end functionality is retained, the arms may be chain extended to give star block copolymers (321). In other cases the dormant functionality can be retained in the core in a manner that allows synthesis of mikto-arm stars (324). 

The Chemistry of Radical Polymerization Tabic 9,29 Star Precursors for NMP... 

I he method of polymerization needs to be chosen for compatibility with functionality in the cores and the monomers to be used. Star block copolymers have also been reported. Mulli(bromo-compounds) may be used directly as ATRP initiators or they can be converted to RAFT agents. One of the most common... 

The two strategies for star synthesis each have advantages and limitations. Star-star coupling only occurs with strategy method (a). The propagating radicals remain attached to the core as shown in Scheme 9.68 for the case of a RAFT polymerization and an example is shown in Figure 9,12a.626... 

The arm-first synthesis of star microgels by initiating polymerization or copolymerization of a divinyl monomer such as diviny lbenzene or a bis-maleimide with a polystyryl alkoxyamine was pioneered by Solomon and coworkers.692 693 The general approach had previously been used in anionic polymerization. The method has now been exploited in conjunction with NMP,692 6 ATRP69 700 and RAFT.449 701 702 The product contains dormant functionality in the core. This can be used as a core for subsequent polymerization of a monoene monomer to yield a mikto-arm star (NMP ATRP704). 

The use of dendritic cores in star polymer synthesis by NMP, ATRP and RAFT polymerization was mentioned in Section 9.9.1, In this section wc describe the synthesis of multi-generation dendritic polymers by an iterative approach. 

Graft copolymers made by living polymerization processes are often called polymer brushes because of the uniformity in graft length that is possible. The basic approaches to graft copolymers also have some analogies with those used in making block and star copolymers. 

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