Sulfonated poly block copolymers

Synthesis of the poly(sodium styrene sulfonate)-/7-polymethyl methacrylate-II-polymethyl Methacrylate-/ -poly(sodium styrene sulfonate) (Plla) block copolymer... 

Fujimoto C. H., Hibbs M., Ambrosini A., Multi-block sulfonated poly(phenylene) copolymer proton exchange membranes, 2012, U.S. Patent 8110636 Bl. 

Poly (ary lene ether sulfone)s and poly(arylene ether ketone) have been employed to prepare block and graft copolymers. Generally, the block copolymers can be prepared by reacting functional-group-terminated oligomers with other functional oligomers and monomers. 

Preparation of polyfethylene oxide) (PEO) and poly(arylene ether) based hydrophilic-hydrophobic block copolymer is of special interest because PEO has been proven to be particularly reliable and versatile for the surface modification of biomaterials. The first poly(ediylene oxide)-/ /oc/c-polysulfonc (PEO-fc-PSF) copolymers were reported by Aksenov et al.217 They employed diisocyanate chemistry to link hydroxy-terminated sulfone oligomers and polyfethylene... 

Siloxane block copolymers, 451 Siloxanes, 450-456 Silyl ether displacement, poly(arylene ether sulfone) synthesis via, 340... 

Vaterite is thermodynamically most unstable in the three crystal structures. Vaterite, however, is expected to be used in various purposes, because it has some features such as high specific surface area, high solubility, high dispersion, and small specific gravity compared with the other two crystal systems. Spherical vaterite crystals have already been reported in the presence of divalent cations [33], a surfactant [bis(2-ethylhexyl)sodium sulfate (AOT)] [32], poly(styrene-sulfonate) [34], poly(vinylalcohol) [13], and double-hydrophilic block copolymers [31]. The control of the particle size of spherical vaterite should be important for application as pigments, fillers and dentifrice. 

Kim, J., Kim, B. and Jung, B. 2002. Proton conductivities and methanol permeabilities of membranes made from partially sulfonated polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene copolymers. Journal of Membrane Science 207 129-137. 

Yang, Y. S., Shi, Z. Q. and Holdcroft, S. 2004. Synthesis of poly[arylene ether sulfone-b-vinylidene fluoride] block copolymers. European Polymer Journal 40 531-541. 

Shi, Z. Q., and Holdcroft, S. 2005. Synthesis and proton conductivity of partially sulfonated poly([vinylidene difluoride-co-hexafluoropropylene]-b-styrene) block copolymers. Macromolecules 38 4193-4201. 

These polymers show lower water uptake than the analogous sulfonated poly(arylene ether sulfone) materials, possibly suggesting some interaction between the aromatic nitrile and sulfonic acid. The phosphine oxide functional moiety could also be used as a compatibilizer with other materials. Sulfonated poly(arylene ether phosphine oxide sulfone) terpoly-mers have been prepared both with sulfonated triphenyl phosphine oxide and with triphenyl phosphine oxide with 3,3 -disulfonate-4,4 —dichlorodiphenyl sulfone as the sulfonic acid bearing monomer. Block copolymers containing phosphine oxide appear to avoid the ether—ether interchange that results when non—phosphine oxide blocks are utilized, and this is being further pursued. ... 

Mani S, Weiss RA, Williams CE, Hahn SF. Microstructure of ionomers based on sulfonated block copolymers of polystyrene and poly(ethylene-afe-propylene). Macromolecules 1999 32 3663-3670. 

Brunell et al. (2) prepared sulfonated poly(polyetherketone-block-polyethersul-fone) derivatives, (II), which had high proton conductivity at 80°C and were used in fuel cells. Random copolymers,... 

Miyaki and Fujimoto and co-workers [16,17] have obtained an even finer distribution of fixed charge groups by casting films from multicomponent block copolymers such as poly(isoprene- >-styrene- >-butadiene- >-(4-vinyl benzyl)dime-thylamine- Msoprene). These films show a very regular domain structure with a 200-500 A spacing. After casting the polymer film, the (4-vinyl benzyl) dimethy-lamine blocks were quatemarized with methyl iodide vapor, and the styrene blocks were sulfonated with chlorosulfuric acid. 

Many works on the synthesis of cyclic polymers and block copolymers using kinetically controlled ring-expansion polymerizations of cyclic monomers, such as lactones and lactides with various types of cyclic tin initiators, were reviewed by Kricheldorf [147,148]. Kricheldorfs group continued the synthesis of cyclic polymers, and their recent works have focused on the following. Polycondensations of 4,4/-difluorodiphenylsulfone with tris(4-hydroxy phenyl)ethane were performed in DMSO to give multi-cyclic poly(ether sulfone)s derived from tris(4-hydroxyphenyl)ethane [149]. 

Sulfonation is very useful chemical modification of polymer, as it induces high polarity in the polymer changing its chemical as well as physical properties. Sulfonated polymers are also important precursors for ionomer formation [75]. There are reports of sulfonation of ethylene-propylene diene terpolymer (EPDM) [76, 77], polyarylene-ether-sulfone [78], polyaromatic ether ketone [79], polyether ether ketone (PEEK) [80], styrene-ethylene-butylene-styrene block copolymer, (SEBS) [81]. Poly [bis(3-methyl phenoxy) phosphozene] [82], Sulfonated polymers show a distinct peak at 1176 cm"1 due to stretching vibration of 0=S=0 in the -S03H group. Another peak appears at 881 cm 1 due to stretching vibration of S-OH bond. However, the position of different vibrational bands due to sulfonation depends on the nature of the cations as well as types of solvents [75, 76]. 

Poly(Arylene Ether Sulfone)-Poly(Aryl Carbonate) Block Copolymers... 

Figure 1. High-temperature mechanical behavior of interfacially prepared bis-A-poly sulfone/bis-A-poly carbonate (10,000/10,000) block copolymer...

Th-FFF can be applied to almost all kinds of synthetic polymers, like polystyrene, polyolefins, polybutadiene, poly(methyl methacrylate), polyisoprene, polysulfone, polycarbonate, nitrocelluloses and even block copolymers [114,194,220]. For some polymers like polyolefins, with a small thermal diffusion coefficient, high temperature Th-FFF has to be applied [221]. Similarly, hydrophilic polymers in water are rarely characterized by Th-FFF, due to the lack of a significant thermal diffusion (exceptions so far poly(ethylene oxide), poly(vi-nyl pyrrolidone) and poly(styrene sulfonate)) [222]. Thus Th-FFF has evolved as a technique for separating synthetic polymers in organic solvents [194]. More recently, both aqueous and non-aqueous particle suspensions, along with mixtures of polymers and particles, have been shown to be separable [215]. 

Recent attempts to prepare 26 by RAFT, however, failed [153]. Double hydrophilic block copolymers of NIPAM and 23e [154], as well as of N,N-diethylacrylamide and 23b [155], were prepared with the CTA benzyl dithiobenzoate, and exhibit LCST and UCST behavior in water. The new polymer 51 is also part of amphiphiUc di- and triblock copolymers [152]. Diblock copolymers with poly(ethylene glycol) methyl ether acrylate, dimethylacry-lamide, or 4-vinylstyrene sulfonate are macrosurfactants with a switch-able hydrophobic block. Triblock copolymers containing additionally 4-vinylbenzoic acid differ in the nature of the hydrophilic part [152]. Near-monodisperse block copolymers of N,N-dimethacrylamide and 49a were synthesized in different ways via macro-CTAs of both monomers as the first step. Such sulfobetaine block polymers form aggregates in pure water but are molecularly dissolved after addition of salt [152,156,157]. 

The amphiphilic diblock copolymer has been synthesized in the group of Stephan Forster (University of Hamburg). It consists of a polystyrene sulfonic acid) block of 144 monomers and a hydrophobic poly(ethylethylene) block of 136 monomers. It is called PSSH-PEE in the following discussion. Synthetic details are described elsewhere [18]. The films of the diblock copolymers are made from pure aqueous polymer solutions without any further surfactant. The concentration of the diblock copolymers is given in gL 1-... 

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