Star microgels

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). 

Connal, L.A., Gurr, P.A., Qiao, G.G., Solomon, D.H. From well defined star-microgels to highly ordered honeycomb films. J. Mater. Chem. 15, 1286—1292 (2005)... 

Figure 9.2 Schematic illustrating the structural differences between statistical and star microgels.

Star microgels have also been produced using a living linear polymer as the arms of the microgel structure, which were prepared first. The living polymer was then reacted with a divinyl cross-linker to form a star microgel consisting of a central core and surrounded by linear polymeric arms. Experimental details are reported elsewhere [8]. 

Yin et al. [73,74] prepared new microgel star amphiphiles and stndied the compression behavior at the air-water interface. Particles were prepared in a two-step process. First, the gel core was synthesized by copolymerization of styrene and divinylbenzene in diox-ane using benzoylperoxide as initiator. Microgel particles 20 run in diameter were obtained. Second, the gel core was grafted with acrylic or methacryUc acid by free radical polymerization, resulting in amphiphilic polymer particles. These particles were spread from a dimethylformamide/chloroform (1 4) solution at the air-water interface. tt-A cnrves indicated low compressibility above lOmNm and collapse pressnres larger than 40 mNm With increase of the hydrophilic component, the molecnlar area of the polymer and the collapse pressure increased. 

The living ALi chains polymerize a small amount of DVB leading to the formation of a star molecule bearing within its core (microgel nodule of DVB) a number of active sites, which is theoretically equal to the number of incorporated A arms. Subsequent addition of monomer B yields the /z-star copolymer. 

Stars with high arm numbers are commonly prepared by the arm-first method. This procedure involves the synthesis of living precursor arms which are then used to initiate the polymerization of a small amount of a difunctional monomer, i.e., for linking. The difunctional monomer produces a crosslinked microgel (nodule), the core for the arms. The number of arms is a complex function of reaction variables. The arm-first method has been widely used in anionic [3-6,32-34], cationic [35-40], and group transfer polymerizations [41] to prepare star polymers having varying arm numbers and compositions. 

In comparison to the polybutadiene stars under similar reaction conditions, the polyisoprene stars showed slightly lower degrees of branching. The added steric hindrance from the methyl group on the polyisoprene anion perhaps makes entry into the DVB "microgel" nodule difficult. 

The first synthesis of star polymers with a microgel core was reported by Sa-wamoto et al. for poly(isobutyl vinyl ether) (poly(IBVE)) [3,4]. In the first step, living cationic polymerization of IBVE was carried out with the HI/ZnI2 initiating system in toluene at -40 °C. Subsequent coupling of the living ends was performed with the various divinyl ethers 1-4. 

Table 1. Multiarm star polymers and copolymers with a microgel core ...

Similarly, the microgel-mediated linking of living poly(isobutene) chains with divinylbenzene gives star-shaped rubbery polymers [213]. The living isobutene polymerization is initiated with a tertiary chloride/TiCl4... 

There are two basic synthetic routes for star polymers (Scheme 12)-the core first method (polymerization from multifunctional initiators or microgels) and the arm first method (where growing polymer chain ends are reacted with a multifunctional terminating agent or a divinyl compound). Whereas the use of multifunctional initiators leads to stars with a well-known (but often low) number of arms, the use of microgels or divinyl compounds leads to a rather broad arm number distribution, where the average arm number can be quite high. 

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