ABA triblocks

The preparation of ABA triblock polymers requires use of a telechelie bisthiol prepared by termination of anionic polymerization initiated by a difunctional initiator. The relative yields of homopolymer, di- and triblock obtained in these experiments depend critically on conversion.273... 

Poly(dimethyl siloxanc) with vinyl or hydrosilanc (Si-H) chain ends have been converted to ATRP initiator ends e.g. Scheme 9.62) by hydrosilylalion, Bis-functional dimethyl siloxane polymers prepared in this way were used in polymerizations of S, MA, tsobornyl acrylate and BA to form ABA triblock copolymers. 

ABA triblock copolymers (as well as multiblock copolymers) cannot be made by sequential addition of monomer A, monomer B, and again monomer A, except in the few cases in which the electron affinity of both monomers is almost the same 27,28, 118>. There are however two ways to circumvent this difficulty ... 

Song, C. X., and Feng, X. D., Synthesis of ABA triblock copolymers of e-caprolactone and DL-lactide, Macromolecules. 

Brzezinska KR, Deming TJ (2001) Synthesis of ABA triblock copolymers via acyclic diene metathesis polymerization and living polymerization of alpha-amino acid-N-carboxyanhy-drides. Macromolecules 34 4348 354... 

Elastomeric Polydiene ABA Triblock Copolymers with Crystalline End Blocks... 

ABA triblock copolymers of the styrene-diene type are well known, and owe their unique properties to their heterophase morphology. This arises from the incompatibility between the polystyrene A blocks and the polydiene B blocks, leading to the formation of a dispersion of very small polystyrene domains within the polydiene matrix. This type of elastic network, held together by the polystyrene "junctions", results in thermoplastic elastomer properties. 

There has been considerable interest recently in an alternative type of ABA triblock structure, where the end blocks could form crystalline domains, by crystallization, rather than amorphous domains by phase separation. It was felt that, since such a crystallization process need not depend on the incompatibility between the blocks, it should be possible to have a homogeneous melt, which should exhibit a much lower viscosity, and hence much easier processing, than the heterogeneous media of the conventional triblock copolymers. Furthermore, thermoplastic... 

The transformation of the chain end active center from one type to another is usually achieved through the successful and efficient end-functionalization reaction of the polymer chain. This end-functionalized polymer can be considered as a macroinitiator capable of initiating the polymerization of another monomer by a different synthetic method. Using a semitelechelic macroinitiator an AB block copolymer is obtained, while with a telechelic macroinitiator an ABA triblock copolymer is provided. The key step of this methodology relies on the success of the transformation reaction. The functionalization process must be 100% efficient, since the presence of unfunctionalized chains leads to a mixture of the desired block copolymer and the unfunctionalized homopolymer. In such a case, control over the molecular characteristics cannot be obtained and an additional purification step is needed. 

ABA triblock copolymers, where A was PBd and B either PS or PMMA were prepared by the combination of ROMP and ATRP techniques [122], The PBd middle blocks were obtained through the ROMP of cyclooctadi-ene in the presence of l,4-chloro-2-butene or cis-2-butene-l,4-diol bis(2-bromo)propionate using a Ru complex as the catalyst. The end allyl chloride or 2-bromopropionyl ester groups were subsequently used for the ATRP of either styrene or MMA using CuX/bpy (X = Cl or Br) as the catalytic system (Scheme 50). Quantitative yields but rather broad molecular weight distributions (Mw/Mn higher than 1.4) were obtained. 

Fig. 4 Mean-field phase diagrams for melts of a AB diblock copolymer r = 0 and b symmetric ABA triblock copolymer (r = 0.5) plotted in terms of segregation /N and composition /a calculated with SCFT. From [32]. Copyright 2000 American Institute of Physics...

The comparison of a linear PS-fr-PI-fr-PS triblock with its linear analogue was performed by Takano et al. [97]. As in the diblock case the cyclic copolymer exhibits a smaller domain spacing however, the effect is not so pronounced (Table 3). This finding may be explained by the tendency of the ABA triblock to exhibit a higher curvature compared to an AB diblock, which in consequence reduces the differences between a cyclic diblock and its linear ABA counterpart. 

Fig. 57 Schematic comparison of chain conformations of the midblock for ABC and ABA triblocks. ABC triblock terpolymers (a) have bridge conformations only, whereas ABA triblock copolymers (b) have bridge and loop conformations. From [159]. Copyright 2002 Wiley...

The use of these initiators to polymerize LA814 and methylglycolide815 has been reported to proceed in a well-controlled fashion. Block copolymers such as PCL-b-PLA have also been prepared. Elimination of PrOH from the reaction of (270) with preformed hydroxyl terminated polymers, followed by lactone polymerization, yields diblocks of CL with polystyrene or polybutadiene.816 The preparation of an ABA triblock has also been reported (A = CL, B = LA) since propagating chains of PLA do not initiate CL ring opening, (270) was pretreated with hydroxy terminated (PCL-b-PLA)-OH 814... 

The differences observed between AB di- and ABA triblock copolymers could be explained because two A blocks must escape from the micellar core in the case of ABA triblock chains. 

Excellent reviews on micelles formed in organic solvents have been published by Hamley [2], Chu et al. [86], and Riess [14]. From these overviews it appears that a wide range of styrene-, (meth)acrylates-, and dienes-based block copolymers were investigated and that the formation of micelles in organic solvents can generally be considered as an entropy-driven process. AB diblock and ABA triblock architectures were systematically compared. All these previous investigations have been summarized by Hamley [2], We will therefore not perform an extensive review of all these systems, since this information has already been provided by others, but we will briefly outline some selected examples. 

Covalently connecting two incompatible polymers at their ends leads to a fascinating class of self-assembling materials [1]. Block copolymers constitute a well-studied and well-documented set of nanostructured hybrid materials [2], Many synthetic techniques are available for generating AB diblock, ABA triblock, ABC triblock and even more complicated block architectures [3,4], Furthermore, the thermodynamics governing the self-assembly... 

ABA triblock copolymers, sometimes referred to as dumbbell shaped copolymers when B is a linear macromolecule. 

ABA triblock hybrids with Frechet-type dendrons as terminal A blocks and polystyrene as the central B block have been prepared by anionic bidirectional growth of polystyrene followed by attachment of reactive dendrons at the chain... 

Figure 7.7 Growth of ABA triblock hybrid by living free radical polymerization...

JH NMR) studies confirmed the presence of the AB diblocks in the product. This determination was facilitated by the fact that the dendritic nitroxide could be differentiated from the nonnitroxide-bearing dendron by NMR spectroscopy. Careful analytical studies confirmed that the pure ABA copolymers could be separated by column chromatography and that the undesired diblock impurity resulted mainly from the loss of the dendritic nitroxide during the course of the reaction. Obviously, this approach to ABA triblocks has rather limited practical value since the thermal stability of the final product is quite low. 

Figure 7.12 Preparation of an amphiphilic ABA triblock hybrid by Williamson ether synthesis...

Some particularities of the extraction of ions from an aqueous organic phase, and of the phase catalyzed polyetherification will be summarized. These will represent the fundamentals of our work on the synthesis of some novel classes of functional polymers and sequential copolymers. Examples will be provided for the synthesis of functional polymers containing only cyclic imino ethers or both cyclic imino ethers as well as their own cationic initiator attached to the same polymer backbone ABA triblock copolymers and (AB)n alternating block copolymers and a novel class of main chain thermotropic liquid crystalline polymers containing functional chain ends, i.e., polyethers. 

Three major topics of research which are based on phase transfer catalyzed reactions will be presented with examples. These refer to the synthesis of functional polymers containing functional groups (i.e., cyclic imino ethers) sensitive both to electrophilic and nucleophilic reagents a novel method for the preparation of regular, segmented, ABA triblock and (A-B)n alternating block copolymers, and the development of a novel class of main chain thermotropic liquid-crystalline polymers, i.e., polyethers. 

Under carefully selected reaction conditions, the polyetherification of an u)-phenol oligomer with an a, o)-di(electrophilic) oligomer produces unexpectedly pure ABA triblock copolymers(11). while the polyetherification of an a, u)-di(electrophilic) oligomer with an a, u)-di (nucleophilic) oligomer represents a new method for the synthesis of perfectly alternating (AB) block copolvmers(9-12.22). 

An example for the synthesis of poly(2,6-dimethyl-l,4-phenylene oxide) - aromatic poly(ether-sulfone) - poly(2,6-dimethyl-1,4-pheny-lene oxide) ABA triblock copolymer is presented in Scheme 6. Quantitative etherification of the two polymer chain ends has been accomplished under mild reaction conditions detailed elsewhere(11). Figure 4 presents the 200 MHz Ir-NMR spectra of the co-(2,6-dimethyl-phenol) poly(2,6-dimethyl-l,4-phenylene oxide), of the 01, w-di(chloroally) aromatic polyether sulfone and of the obtained ABA triblock copolymers as convincing evidence for the quantitative reaction of the parent pol3rmers chain ends. Additional evidence for the very clean synthetic procedure comes from the gel permeation chromatograms of the two starting oligomers and of the obtained ABA triblock copolymer presented in Figure 5. 

Table 4. Tensile properties of the poly(CL-[7-DXO-[7-CL) ABA triblock copolymers (see Scheme 39) ...

To sum up, the living character of the aluminum alkoxide mediated ROP of lactones has permitted the synthesis of novel ABA triblock copolymers, the composition and molecular weight of which can purposely be tuned up for displaying excellent elastomeric properties. Interestingly, the inherent biodegradability of each partner, PCL and PDXO, would open up new applications for these novel thermoplastic elastomers. 

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