Triblock terpolymers

Further work related to the synthesis of copolymers with either P2VP or P4VP blocks has been reported in the literature. Triblock terpolymers PS-fc-P2VP-fo-PEO were synthesized in THF at - 78 °C by sequential polymerization of styrene and 2VP, initiated by s-BuLi in the presence of IiCl [25]. The living polymer was terminated with EO. The end-hydroxyl group was... 

Triblock terpolymers PS-b-PBd-b-P2VP and PBd-b-PS-b-P2VP, where PBd is polybutadiene (mostly 1,2-PBd), were prepared in order to study the microphase separation by transmission electron microscopy, TEM and SAXS. In the first case the triblocks were synthesized by the sequential addition of monomers in THF using s-BuLi as the initiator [26]. For the second type of copolymers, living PBd-b-PS diblocks were prepared in benzene at 40 °C in the presence of a small quantity of THF in order to obtain the desired 1,2-content and to accelerate the crossover reaction as well. DPE was then added to decrease the nucleophilicity of the active centers in order to avoid side reactions with the THF, which in combination with benzene was the solvent of the final step. 

Multiblock copolymeric structures containing PCHD blocks were also synthesized using s-BuLi as the initiator and either TMEDA or DABCO as the additive. Sequential monomer addition was performed with CHD being the last monomer added in all cases [35]. The structures prepared are PS-b-PCHD, PI-fc-PCHD and PBd-b-PCHD block copolymers, PS-fo-PBd-fo-PCHD, PBd-fr-PS-b-PCHD and PBd-fo-PI-fr-PCHD triblock terpolymers, and PS-fc-... 

ABC, ACB, and BAC triblock terpolymers, where A is PMMA, B is PDMAEMA, and C is poly[hexa(ethylene glycol)methacrylate], PHEGMA, were synthesized via GTP and sequential monomer addition [89]. The polymerizations were conducted in THF using MTS and TBABB as the initiator... 

The triblock terpolymer polypropylene oxide)-h-poly[2-(dimethylami-no)ethyl methacrylate]-b-poly[oligo(ethylene glycol) methacrylate], PPO-fc-PDMAEMA-fc-POEGMA, was prepared using the PPO macroinitiator followed by the addition of CuCl, HMTETA, and DMAEMA for the polymerization of the second block and finally OEGMA for the synthesis of the final product (Scheme 54) [128]. 

The same heterobifunctional initiator, 2-phenyl-2-[(2,2,6,6-tetramethy-piperidino)oxy] ethyl 2-bromo-2-methyl propanoate, was employed for the synthesis of PMMA-fo-PfBuA-fo-PS triblock terpolymers via the combination of ATRP and NMP [136]. Styrene was initially polymerized through the alkoxyamine function in bulk at 125 °C, leading to PS chains with bromine end groups. Subsequent addition of fBuA in the presence of CuBr/PMDETA provided the PS-fr-PfBuA diblock. Further addition of CuCl, to achieve halogen exchange and MMA yielded the desired triblock copolymer with... 

Anionic polymerization techniques were also critical for the synthesis of a model cyclic triblock terpolymer [cyclic(S-fo-I-fr-MMA)] [196]. The linear cctw-amino acid precursor S-fr-I-fr-MMA was synthesized by the sequential anionic polymerization of St, I and MMA with 2,2,5,5-tetramethyl-l-(3-lithiopropyl)-l-aza-2,5-disilacyclopentane as the initiator and amine generator, and 4-bromo-l,l,l-trimethoxybutane as a terminator and carboxylic acid generator. Characterization studies of the intermediate materials as well as of the final cyclic terpolymer revealed high molecular and compositional homogeneity. Additional proof for the formation of the cyclic structure was provided by the lower intrinsic viscosity found for the cyclic terpolymer compared to that of the precursor. 

A systematic comparative study of triblock terpolymers in the bulk and thin-film state was carried out on polystyrene-fo-poly(2-vinyl pyridine)-b-poly(ferf-bulyl methacrylate), PS-fr-P2VP-fr-PfBMA. A diblock precursor with a minority of PS leading to a double gyroid structure was used. Upon increase of PfBMA content this morphology changed from lamellae with... 

Fig. 13 Phase diagram of synthesized PS-fc-P2VP-fc-PtBMA triblock terpolymers. From [64], Copyright 2003 Elsevier...

A triblock terpolymer consisting of polyisoprene, deuterated PS and poly(vinyl methyl ether) shows a UCST behaviour between the first two blocks and an LOST behaviour between the last two blocks. Although the UCST was not... 

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...

Addition of the middle B block to an ABC triblock terpolymer has been investigated by Suzuki et al. for the PI- -PS- -P2VP system [ 159]. Starting from the lamellar structure of the unblended triblock (0ps = 0.42) PS homopolymer was subsequently added. At fas 0.50 a morphological transformation into a gryoid structure is observed. Even if the volume fraction of PS is increased up to fas = 0.60, the cell size of the gyroid structure will remain... 

Fig. 58 Lattice constants vs. volume fractions of PS phase for a blending a PI-0-PS-0-P2VP triblock terpolymer with PS homopolymer (blends I and II) and b blending a Pl-fr-PS-fr-P2VP triblock terpolymer with PI and P2VP homopolymers (blends III and IV). Arrows variations of ps with increasing volume fractions of added homopolymers. , , lattice constants of pure triblock terpolymers o, , A lattice constants of blends. Gray band between a and b expresses experimentally obtained microphase separation phase diagram for unblendend PI-6-PS-6-P2VP. From [159], Copyright 2002 Wiley...

Some work has been done on blends of ABC and AB or AC or AB C block copolymers, such as polystyrene-b-polybutadiene-b-poly(methyl methacrylate) (PS-h-PB-fc-PMMA) triblock terpolymers with PS-h-PB or PB-h-PMMA or other systems. Besides known morphologies for these block copolymers (though at other overall compositions with respect to the different chemical... 

Attractive interactions are also the reason for the self-assembly of PS-fo-PB-fo-PMMA at the interface of poly(styrene-co-acrylonitrile), SAN, and poly(2,6-dimethylphenylene ether), PPE. In this blend, PS and PPE are miscible on one side and PMMA and SAN are miscible on the other one, with negative / parameters. This blend, in which the rubbery domain is located at the interface between SAN/PMMA and PPE/PS, was originally prepared by coprecipitation of all components from a common solution [195]. From a processing point of view, in this system the difficulty was to get the dispersion of PPE in SAN via melt mixing of SAN, PPE and the triblock terpolymer. 

Ludwigs S, Schmidt K, Stafford CM, Amis EJ, Fasolka MJ, Karim A, Magerle R, Krausch G (2005) Combinatorial mapping of the phase behavior of ABC triblock terpolymers in thin films Experiments. Macromolecules 38 1850-1858... 

In order to overcome the build-up of these stresses, the addition of triblock terpolymers as compatibilizing agents with an elastomeric middle block and end blocks of PS and PMMA, respectively, appears advantageous. One example is the use of polystyrene-Wocfc-poly(l,4-butadiene)-W0cfc-poly(methyl methacrylate)... 

Fig. 15 Schematic of the morphological arrangement in PPE/SAN blends compatibilized by SBM triblock terpolymers - nanostructured raspberry morphology (reprinted from [45])...

SBM) as a compatibilizer. As a result of the particular thermodynamic interaction between the relevant blocks and the blend components, a discontinuous and nanoscale distribution of the elastomer at the interface, the so-called raspberry morphology, is observed (Fig. 15). Similar morphologies have also been observed when using triblock terpolymers with hydrogenated middle blocks (polystyrene-W<9ck-poly(ethylene-C0-butylene)-Wock-poly(methyl methacrylate), SEBM). It is this discontinuous interfacial coverage by the elastomer as compared to a continuous layer which allows one to minimize the loss in modulus and to ensure toughening of the PPE/SAN blend [69],... 

The aim of this section, therefore, is to correlate systematically the compatibilization of PPE/SAN 60/40 blends by SBM triblock terpolymers with the foaming behavior of the resulting blend. The reduction of the blend phase size, the improved phase adhesion, a potentially higher nucleation activity of the nanostructured interfaces, and the possibility to adjust the glass transitional behavior between PPE and SAN, they all promise to enhance the foam processing of PPE/SAN blends. 

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