Star core-first technique

The core-first method, which uses an active multifimctional core to initiate growth of polymer chains, was apphcable to make hybrid POSS-core star-shaped polyoxazohnes that showed an increase in Tg, compared to that of polyoxazohne initiated by methyl p-toluenesulfonate (MeOTs) with poly(2-methyl-2-oxazohne) (POZO) [76]. Other hybrid star-shaped polyoxazohnes initiated by cube-OTs or cube-benzyl revealed the same phenomenon. This was attributed to the reduction of segmental mobifity of POZO in starshaped polyoxazolines, which was caused by the incorporation of hard, compact POSS moiety to the core of star polymer with the core-first technique. The conclusions were drawn that the thermal stabilities of star-shaped polymers increased as the POSS wt % was increased, and this was used as a measure of the effect of the inorganic POSS unit on polymer thermal properties. 

Generally, there are two strategies to prepare star polymers the core-first strategy [37-44], and the arm-first strategy [45-52], The arm-first strategy starts with the linear arms first. Since the arms are prepared separately, many living/controlled polymerization techniques can be employed. Thus, the linear arms can be synthesized in a defined manner. Then one of the chain ends will be functionalized for further crosslinking reactions. Based on the functionalities of the chain ends, the arm-first methods can be divided into macroinitiator (MI) method and macromonomer (MM) method. 

Based on the findings of the arm-first strategy, it is possible to obtain stars with well-defined arm length. The main problem of this strategy is the arm number distribution. Moreover, purification may cause many difficulties in the synthesis. In contrast, the core-first strategy requires multifunctional initiators and further polymerization initiated from the core. This is shown in Scheme 3. The maximum arm numbers of the stars are determined by the number of functionalities in the core. In the ideal case, the initiating efficiency of the core is close to unity, which will produce well-defined stars with precise numbers of arms. However, due to the steric hindrance and the limit of the polymerization techniques, it can be difficult to obtain full initiating efficiency. 

The first step for the core-first stars is the synthesis of multifunctional initiators. Since it is difficult to prepare initiators that tolerate the conditions of ionic polymerization, mostly the initiators are designed for controlled radical polymerization. Calixarenes [39, 58-61], sugars (glucose, saccharose, or cyclodextrins) [62-68], and silsesquioxane NPs [28, 69] have been employed as cores for various star polymers. For the growth of the arms, mostly controlled radical polymerizations were used. There are only very rare cases of stars made from nitroxide-mediated radical polymerization (NMRP) [70] or reversible addition-fragmentation chain transfer (RAFT) techniques [71,72], In the RAFT technique one has to differentiate between approaches where the chain transfer agent is attached by its R- or Z-function. ATRP is the most frequently used technique to build various star polymers [27, 28],... 

Controlled polymerization techniques have enabled the preparation of well-defined polyelectrolytes of different architectures. Polyelectrolyte stars and cylindrical brushes are two typical examples with isotropic and anisotropic nature, respectively. Different synthetic strategies have been developed for these polyelectrolytes. However, the core first and grafting from strategies have turned out to be the most suitable methods for the synthesis of polyelectrolyte stars and cylindrical brushes. 

In this case, the chains are grown away from the core, and attached when undergoing transfer reactions hence, stars only contain branches in a dormant form. One advantage of this technique is that complications such as star-star couplings, as encountered in the core-first star synthesis, can be avoided. A potential problem, however, is the reduced accessibility to the RAFT moieties of the core by polymeric arms (shielding effect). Some typical multifunctional RAFT agents used in the Z-approach are shown in Figure 27.4. 

This method is similar to the arm-first approach, but the same technique can be applied as a core-first approach. In this case, a monofunctional initiator reacts with the difunctional monomer, leading to the formation of tightly cross-linked miaogel nodules bearing active sites that can be used for the polymerization of a suitable monomer. High-funaionality stars can be prepared by this method however, the disadvantages and restrictions reported previously also apply in this case. 

Miktoarm polymers are essentially heteroarm star polymers where two or more arms of the star are chemically unique. Therefore, the same general approaches for the synthesis of star polymers also apply to miktoarms, with some additional constraints. Many research groups have sequentially performed orthogonal polymerization techniques to access a variety ABC and ABCD miktoarm polymers, in a core-first approach. 

The divergent or core-first method This consists of the initiation of a controlled polymerization from a multifunctional initiator, which serves finally as the star central core. This technique requires a controlled and quantitative initiation followed by a living-like polymerization process without transfer or termination. In most cases, stars obtained by this approach possess a limited number of branches typically between three to five or six. A precise determination of the number of star branches using conventional characterization techniques is not easy and generally average values can be obtained. 

Star polymers generated using the core-first method have a large distribution in functionalities. To minimize the distribution in functionalities of the stars, the in-out technique was developed. The in-out method is a combination of the two techniques mentioned above and first generates a small arm-first star with living active sites, then uses this core to initiate the polymerization of the star branches. The resulting stars can be functionalized, and the control over the distribution in functionalities is greatly improved. 

Many different approaches have been used to synthesize star-block copolymers including anionic, cationic, radical, and condensation polymerization techniques, and even combinations of them [9]. The majority of the molecules produced thus far were prepared by anionic polymerization procedures. The dominant way of preparing star-block copolymers by anionic polymerization is the coupling of preformed diblock or triblock living copolymer chains with a suitable compound to produce the central linking point. In this way divinylbenzene (DVB) was first used in order for a central core to be created [ 10]. This was achieved by adding a predetermined amount of the divinyl compound to a solution of living diblock chains (Scheme 1). 

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