Terpolymers, synthesis

B.M. Rao, P.R. Rao, and B. Sreenivasulu, Grafting of maleic anhydride onto acrylonitrile-butadiene-styrene terpolymer Synthesis and characterization, Polym.-Plast. Technol. Eng., 38(5) 967-977, November 1999. 

Hadjichristidis N, Iatrou H et al (2005) Linear and non-linear triblock terpolymers. Synthesis, self-assembly in selective solvents and in bulk. Progr Polym Sci 30 725-782... 

Vinylpyridine (23) came into prominence around 1950 as a component of latex. Butadiene and styrene monomers were used with (23) to make a terpolymer that bonded fabric cords to the mbber matrix of automobile tires (25). More recendy, the abiUty of (23) to act as a Michael acceptor has been exploited in a synthesis of 4-dimethylaminopyridine (DMAP) (24) (26). The sequence consists of a Michael addition of (23) to 4-cyanopyridine (15), replacement of the 4-cyano substituent by dimethylamine (taking advantage of the activation of the cyano group by quatemization of the pyridine ring), and base-cataly2ed dequatemization (retro Michael addition). 4-r)imethyl aminopyri dine is one of the most effective acylation catalysts known (27). 

Han S.J., Lohse D.J., Radosz M., and Sperling L.H. Thermoplastic vulcanizates from isotactic olypro-pylene and ethylene-propylene-diene terpolymer in supercritical propane Synthesis and morphology. Macromolecules, 31, 5407, 1998. 

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... 

An allyl samarocene catalyst, [(CMe2C5H4)2SmCl(C3H5)MgCl2(THF)4, was employed for the synthesis of trans-Vl-b-VCL copolymers and poly(fra s-isoprene-co-hex-l-ene)-fr-PCL terpolymers [111]. The copolymerizations... 

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... 

The oxocarbenium perchlorate C(CH20CH2CH2C0+C104 )4 was employed as a tetrafunctional initiator for the synthesis of PTHF 4-arm stars [146]. The living ends were subsequently reacted either with sodium bromoacetate or bromoisobutyryl chloride. The end-capping reaction was not efficient in the first case (lower than 45%). Therefore, the second procedure was the method of choice for the synthesis of the bromoisobutyryl star-shaped macroinitiators. In the presence of CuCl/bpy the ATRP of styrene was initiated in bulk, leading to the formation of (PTHF-fc-PS)4 star-block copolymers. Further addition of MMA provided the (PTHF-fr-PS-fc-PMMA)4 star-block terpolymers. Relatively narrow molecular weight distributions were obtained with this synthetic procedure. 

By utilizing a combination of RAFT and cationic ROP, the synthesis of [poly(methyl methacrylate)][poly(l,3-dioxepane)][polystyrene] miktoarm star terpolymers was achieved [182], The approach involved the synthesis of PS functionalized with a dithiobenzoate group by RAFT polymerization and subsequent reaction with hydroxyethylene cinnamate (Scheme 98). The newly created hydroxyl group was then used for the cationic ring opening polymerization of 1,3-dioxepane (DOP). The remaining dithiobenzoate group was used for the RAFT polymerization of methyl methacrylate. 

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. 

An interesting way to prepare shock-resistant coatings [381] follows the synthesis of the ABS-terpolymers, e.g. shock-resistant polystyrene, where a soft, elastomeric phase is incorporated in a hard polymer matrix via covalent bonds. Because organic coatings solidify in situ, elastomeric microgels have been synthesized and mixed to a binder which forms the hard matrix phase before the application of this mixture as a coating material. 

Song P, Xiao M, Wang S, Du E, Meng Y (2009) Synthesis and properties of terpolymers derived from carbon dioxide, propylene oxide and phthalic anhydride. Gaofenzi Cailiao Kexue Yu Gongcheng 25(8) ... 

Research Focus Synthesis of amphiphilic terpolymers containing ethylene oxide and (R)-3-hydroxybutyrate and hydrogels containing cyclodextrin. Originality Ongoing 3-year investigation. 

Wamsley, A., Jasti, B., Phiasivongsa, P., and Li, X. Synthesis of random terpolymers and determination of reactivity ratios of IV-carboxyanhydrides of leucine, (1-benzyl aspartate, and valine. J. Polymer Sci. [A] Polymer Chem. 42 317—325, 2004. 

The largest proportion of TFE is used for the polymerization into a variety of PITH homopolymers. It is also used as comonomer in the copolymerization with hexaflu-oropropylene, ethylene, perfluorinated ether, and other monomers and also as a comonomer in a variety of terpolymers. Other uses of TFE are to prepare low-molecular-weight polyfluorocarbons, carbonyl fluoride oils, as well as to form PTFE in situ on metal surfaces,13 and in the synthesis of hexafluoropropylene, perfluorinated ethers, and other oligomers.14... 

Miktoarm star terpolymers of the type ABC have been prepared by several methods. Iatrou and Hadjichristidis reported the synthesis of a miktoarm star consisting of PS, PI and PB branches radiating from the star center [51]. This was achieved using the chlorosilane method and the step by step linking of the different branches to the trichloromethylsilane, which was the linking agent, as shown in Scheme 19. 

Only one case concerning the synthesis of a miktoarm star quaterpolymer has appeared in the literature. It consists of four different branches, namely PS, po-ly(4-methyl styrene) (P4MeS), PI and PB [35]. The reaction sequence for the preparation of this miktoarm star is presented in Scheme 23. The procedure was similar to the one adopted for the synthesis of the ABC-type terpolymers by the chlorosilane method. The characteristic of this method is that two of the arms were incorporated to the linking agent by titration. Consequently the order of addition plays an important role for the preparation of well defined products. PS was chosen to react first with an excess of SiCl4, followed after the evaporation of the excess silane, by the titration with the more sterically hindered P4MeS so that only one arm can be incorporated in the star. The moderately hindered PILi anion was then added by titration, followed by the addition of the fourth arm, which is the least sterically hindered PBLi anion so that complete linking can be achieved. The reaction sequence was monitored by SEC and these results in combination with the molecular and spectroscopic characterization data showed that well defined quaterpolymers were prepared. 

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