Poly ionene

Sassoon and Rabani [79, 83] constructed an intriguing photoinduced ET system in which the back ET was greatly retarded by the electrostatic repulsion between two different polycations. They prepared poly(3,3-ionene) covalently linked with Ru(bpy)f + (26) and with an iY,Af,/V, Ar -tetraalkyl-/>-phenylenediamine derivative (27). The latter is an electron donor quencher toward the photoexcited Ru(II) complex. 

Poly(3,3 ionene) 80 Polylysine 148 Polymethacrylic acid 54 Polypeptides 147 Polypropylene oxide 158 Polysoaps 63... 

Inouye, K. Murata, K. Ishikawa,T. (1971) Ef fekt von Cu(II)-Ionen auf die Magnetbildung einer aus Eisen-II- und Eisen-III-hydroxid bestehenden Mischung. Kolloid-Z. u. Z. Poly-mere 250 262-263... 

Wilkes and coworkers studied polyrotaxanes derived from self-assembly of a polyurethane bearing paraquat moieties and BPP34C10 [130b]. The polyurethanes contained soft (poly(tetramethylene oxide)) and hard (paraquat ionene) segments. Interestingly, dynamic mechanical analysis indicated that polyrotaxanes had higher rubbery plateau moduli than the corresponding backbones. Thermal analysis revealed that the stability was enhanced by the formation of the polyrotaxanes. 

PAA = poly (acrylic acid), PMAA = poly(methacrylic acid), PI A = poly(itaconic acid), PGA = poly(L-glutamic acid), QPVP = poly(N-ethyl-4-vinyl-pyridinium bromide), PLL = poly(L-lysine), PDMAEMA = poly(2-N,N-dimethylaminoethyl methacrylate), PVBMA = poly(4-vinylbenzyl-trimethylammonium chloride), 5,6-ionene, 2,5-ionene, 10,10-ionene, 2X and 3X (see text)... 

When the degree of neutralization (i.e. the pH of the solution) of a weak polyelectrolyte is changed, the composition of the polyelectrolyte complexes containing a polycation is varied as in the resulting systems of some poly(car-boxylix acid)s-ionenes shown in Fig. 7. On the assumption that the polyelectrolyte complexes are formed upon complete neutralization, their compositions r are denoted by the following equations ... 

Fig, 12 a, b. Effect of ionic strength on the formation of polyelectrolyte complexes (a) Reduced viscosity, (b) transmittance Poly(methacrylic acid) (PMAA) (degree of neutralization of PMAA a = l)-Ionene-type polycation (2X), O PMAA(a = 0.75)-2X, 3 PMAA(a = 0.5)-2X, Poly(acrylic acid) (tz = 1)-2X, A Poly(sodium styrenesulfonate)-2X... 

Fig. 13. Dependence of the composition of the polyelectrolyte complex of poly(methacrylic acid) (PMAA)-ionene-type polycation (2X) on the concentration of the complex O Degree of neutralization of PMAA (a) = 0, ionic strength ( ) = 0, a = 0,fi = 0.01, Aa = l,/i=0, Aa=l,iu = 0.01...

Fig. 46a, b. Time dependence of the complexation. (a) conformational changes of the polymer components in the complexes Poly(L-glutamic acid) (PGA)-tetraethylenepentamine, O PGA-pentaethylenehexamine (b) pH change of the complex solutions Poly(acrylic acid) (PAA)-integral-type polycation (10,10-ionene) O PAA-poly(N-vinyl-2-pyrrolidone) (PVPo)... 

The formation of a water-soluble complex of poly(sodium acrylate) with 5,6 ionen bromide of 3 1 composition has been observed108. Its mass and size are independent of the complex origin and are equal to 660 x 103 and 33 nm respectively. The soluble complex presumably consists of the insoluble nucleus of the equimolar polyelectrolyte complex and adsorbed excess of poly(sodium acrylate) on its surface. The soluble polyelectrolyte complex dissociates at higher ionic strengths (0.05-0.1) whereas the insoluble equimolar complex in the core is still stable and precipitates from the solution. 

A large number of macromolecules complementary to PMAA, namely polyvinylpyrrolidone, polyvinylpyridine, polyacrylamide, poly(vinyl alcohol), poly(ethylene oxide), oligoethylenimine, poly(sodium styrene sulfonate), polycations of the integral type ionen (2X) were used as P2 and P3. The pH of the media strongly influences the studied reactions of complex formation. For example, in PVPy + PVP + PMAA or OEI + PEO + PMAA systems in the add region, where weak polybases are completely protonized and PMAA does practically not dissodate, complexes with hydrogen bonds (PMAA-PVP or PMAA-PEO) are formed. In neutral medium weak polybases are partially ionizated and polyelectrolyte complexes (PMAA-PVPy, PMAA-OEI) are generated. In the alkaline medium formation of complexes has not been observed. 

Among the limited examples of polymers originated by path b (Fig. 153), the polymerization- of diallylamino Mannich bases leading to poly(pyrrolidine)s 397 (Fig. 155) is worth mentioning. The synthesis of ionene polymers of the type 398, used in water clarification, by reaaion between /ran.v-l,4-dichloro-2-butene and a phenolic Mannich base,- is also interesting. 

Polysulfobetaines derived from alternating styrene-maleic anhydride copolymers 32 are easily prepared by ring opening of the anhydride moiety with 3-dimethylaminopropylamine, imidizing the resulting poly(amic acid) by heating, and alkylation with propane sultone [70-72]. For investigations of structure-property relationships additionally to 32b, the polymers 33 and 34 were synthesized [71]. The ionene-like polymer 33 was prepared... 

Osada et al. [252] studied the complexation of 23b with poly(2-acrylamido-2-methylpropanesulfonic acid) (polyAMPS), quaternized polyN-[3-(dime-thylamino)propyl]acrylamide chloride (PDMAPAA-Q), and x,y-ionene bromides (x = 3,6 = 3,4) in aqueous solution. Depending on the concentration and the mixing ratio of the constituent polymers, water-soluble IPCs were formed which exhibit an UCST, Uke the parent polybetaine. The UCST decreased markedly when a small amount of the polyanion polyAMPS was added to the solution of 23b, and eventually disappeared at high concentrations of polyAMPS. 

T. Hasimoto, S. Kohjiya, S. Yamashita, and M. Me, Photochromic and photochemical ionene elastomer containing poly(tetrahydrofuran) segments and viologen units. J. Polym. Sci., Polym. Chem. 29, 651-665 (1991). 

High-molecular mass surfactants such as butyl acrylate-butyl methacrylate-methacrylic acid copolymer sodium salts, starburst dendrimers, poly(amidoamines), and diaminobutane-based poly(propyleneimine) as well as cationic polyelectrolytes (ionenes) had all been presented as successful secondary phases for aromatic compounds. The determination of 10 nitrophenols in glycine buffers modified by 3-CD (0-10 mmolL" ) and polyvinylpyrrolidone (PVP) (0.5-2.5% w/v) is an example of application of polymer-based electrolytes to rain, tap, and process water. ... 

Figure 23-7. Coacervate formation (A and B) or solubilization (C and D) on mixing the polyanion of poly(sodium styrene sulfonate) S with poly(4-vinyl pyridinium hydrogen bromide) P or the ionene Y, or vice versa.

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