Multifunctional Block Copolymers

Jia, Z.F. Wong, L.J. Davis, T.P. Bulmus, V. One-pot conversion of RAFT-generated multifunctional block copolymers of HPMA to doxorubicin conjugated acid- and reductant-sensitive crosslinked micelles. Biomacromolecules 2008, 9 (11), 3106-3113. 

Ambade AV, Burd C, Higley MN, Nair KP, Week M (2009) Orthogonally self-assembled multifunctional block copolymers. Chem Eur J 15(44) 11904—11911... 

Knowledge of kui/kii is also important in designing polymer syntheses. For example, in the preparation of block copolymers using polymeric or multifunctional initiators (Section 7.6.1), ABA or AB blocks may be formed depending on whether termination involves combination or disproportionation respectively. The relative importance of combination and disproportionation is also important in the analysts of polymerization kinetics and, in particular, in the derivation of rate parameters. 

The multifunctional initiators may be di- and tri-, azo- or peroxy-compounds of defined structure (c.g. 20256) or they may be polymeric azo- or peroxy-compounds where the radical generating functions may be present as side chains 57 or as part of the polymer backbone."58"261 Thus, amphiphilic block copolymers were synthesized using the polymeric initiator 21 formed from the reaction between an a,to-diol and AIBN (Scheme 7.22).26 Some further examples of multifunctional initiators were mentioned in Section 3.3.3.2. It is also possible to produce less well-defined multifunctional initiators containing peroxide functionality from a polymer substrate by autoxidalion or by ozonolysis.-0... 

Puskas, J.E., Pattern, W.E., Wetmore, P.M., and Krukonis, A. Multiarm-star polyisobutylene-polystyrene thermoplastic elastomers from a novel multifunctional initiator, Polym. Mater. Set Eng., 82,42 3, 1999. Brister, L.B., Puskas, J.E., and Tzaras, E. Star-branched PIB/poly(p-t-bu-Styrene) block copolymers from a novel epoxide initiator, Polym. Prepr., 40, 141-142, 1999. 

Hexaepoxy squalene, HES (Scheme 70) was used as a multifunctional initiator in the presence of TiCU as a coinitiator, di-f-butylpyridine as a proton trap, and N,N-dimethylacetamide as an electron pair donor in methylcy-clohexane/methyl chloride solvent mixtures at - 80 °C for the synthesis of (PIB-fc-PS)n star-block copolymers [145]. IB was polymerized first followed by the addition of styrene. The efficiency and the functionality of the initiator were greatly influenced by both the HES/IB ratio and the concentration ofTiCL, thus indicating that all epoxy initiation sites were not equivalent for polymerization. Depending on the reaction conditions stars with 3 to 10 arms were synthesized. The molecular weight distribution of the initial PIB stars was fairly narrow (Mw/Mn < 1.2), but it was sufficiently increased after the polymerization of styrene (1.32 < Mw/Mn < 1.88). 

Benzenetricarbonyl trichloride and l,2,4,5-tetrakis(bromomethyl) benzene were employed as multifunctional initiators for the synthesis of 3-and 4-arm PTHF stars, respectively [147]. The living ends were reacted with sodium 2-bromoisobutyrate followed by reduction with Sml2. The samarium enolates, thus formed were efficient initiators for the polymerization of MMA to give the (PTHF-fo-PMMA) , n = 3 or 4 star-block copolymers, according to Scheme 71. 

A combination of anionic and ATRP was employed for the synthesis of (PEO-b-PS) , n = 3, 4 star-block copolymers [148]. 2-Hydroxymethyl-l,3-propanediol was used as the initiator for the synthesis of the 3-arm PEO star. The hydroxyl functions were activated by diphenylmethyl potassium, DPMK in DMSO as the solvent. Only 20% of the stoichiometric quantity of DPMK was used to prevent a very fast polymerization of EO. Employing pentaerythritol as the multifunctional initiator a 4-arm PEO star was obtained. Well-defined products were provided in both cases. The hydroxyl end groups of the star polymers were activated with D PM K and reacted with an excess of 2-bromopropionylbro-mide at room temperature. Using these 2-bromopropionate-ended PEO stars in the presence of CuBr/bpy the ATRP of styrene was conducted in bulk at 100 °C, leading to the synthesis of the star-block copolymers with relatively narrow molecular weight distributions (Scheme 72). 

Recent developments in polymer chemistry have allowed for the synthesis of a remarkable range of well-defined block copolymers with a high degree of molecular, compositional, and structural homogeneity. These developments are mainly due to the improvement of known polymerization techniques and their combination. Parallel advancements in characterization methods have been critical for the identification of optimum conditions for the synthesis of such materials. The availability of these well-defined block copolymers will facilitate studies in many fields of polymer physics and will provide the opportunity to better explore structure-property relationships which are of fundamental importance for hi-tech applications, such as high temperature separation membranes, drug delivery systems, photonics, multifunctional sensors, nanoreactors, nanopatterning, memory devices etc. 

Interestingly, the Fe2+ ion in the core can be easily removed by base, the complex dissociates and the individual polymer dimers can be analyzed. Block copolymers of 2-ethyl-2-oxazoline with other substituted oxazolines have also been made [121]. Ru2+(4,4 dichloromethyl-2,2 bipyridine)3 has also been used as the multifunctional initiator for the ATRP of styrene at 110°C [122], It is interesting to note that the Cu+ ions necessary for the polymerization reaction are solubilized via complexation with other bipyridine species. 

ATRP is a very potent method for preparing block copolymers by sequential monomer addition as well as star polymers using multifunctional initators. Furthermore, it can be applied also in heterogenous polymerization systems, e.g., emulsion or dispersion polymerization. In Example 3-15 the ATRP of MMA in miniemulsion (see also Sect. 2.2A.2) is described. 

Different architectures, such as block copolymers, crosslinked microparticles, hyperbranched polymers and dendrimers, have emerged (Fig. 7.11). Crosslinked microparticles ( microgels ) can be described as polymer particles with sizes in the submicrometer range and with particular characteristics, such as permanent shape, surface area, and solubility. The use of dispersion/emulsion aqueous or nonaqueous copolymerizations of formulations containing adequate concentrations of multifunctional monomers is the most practical and controllable way of manufacturing micro-gel-based systems (Funke et al., 1998). The sizes of CMP prepared in this way vary between 50 and 300 nm. Functional groups are either distributed in the whole CMP or are grafted onto the surface (core-shell, CS particles). 

Since soluble multifunctional initiators are more readily available in cationic polymerization than in the anionic counterpart, ABA type linear triblock copolymers have been almost exclusively prepared using difunctional initiation followed by sequential monomer addition. The preparation and properties of ABA type block copolymer thermoplastic elastomers (TPEs), where the middle segment is PIB, have been reviewed recently [47]. 

Cationic synthesis of block copolymers with non-linear architectures has been reviewed recently [72]. These block copolymers have served as model materials for systematic studies on architecture/property relationships of macromolecules. (AB)n type star-block copolymers, where n represents the number of arms, have been prepared by the living cationic polymerization using three different methods (i) via multifunctional initiators, (ii) via multifunctional coupling agents, and (iii) via linking agents. 

ADMET is a step growth polymerization in which all double bonds present can react in secondary metathesis events. However, olefin metathesis can be performed in a very selective manner by correct choice of the olefinic partner, and thus, the ADMET of a,co-dienes containing two different olefins (one of which has low homodimerization tendency) can lead to a head-to-tail ADMET polymerization. In this regard, terminal double bonds have been classified as Type I olefins (fast homodimerization) and acrylates as Type II (unlikely homodimerization), and it has been shown that CM reactions between Types I and II olefins take place with high CM selectivity [142], This has been applied in the ADMET of a monomer derived from 10-undecenol containing an acrylate and a terminal double bond (undec-10-en-l-yl acrylate) [143]. Thus, the ADMET of undec-10-en-l-yl acrylate in the presence of 0.5 mol% of C5 at 40°C provided a polymer with 97% of CM selectivity. The high selectivity of this reaction was used for the synthesis of block copolymers and star-shaped polymers using mono- and multifunctional acrylates as selective chain stoppers. 

The synthesis of star polymer and star block copolymers with multifunctional initiators are detailed in Table 2. 

The radical mechanism generates block copolymers mainly by means of multifunctional or polymeric initiators [270] or by the combination of radical chain ends produced by the separation of two propagating monomers into an aqueous and a micellar phase (in emulsion) [271],... 

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