AMINE POLYMER

Until 1990 the EPA maintained a Hst of chemicals suitable for potable water treatment ia the United States. Siace then the entire question of certification and standards has been turned over to a group of organi2ations headed by the National Sanitation Eoundation, which has issued voluntary standards. As of January 1992, standards had been issued for most of the principal inorganic products, but only for two polymers, poly(DADMAC) and Epi-DMA (epichl orohydrin dimethyl amine) polymers (78). Certifications for commercial products meeting specified standards are issued by the National Sanitation Eoundation, Underwriter Laboratories, and Risk Eocus/Versar (79). 

The oxidation of poly(N-phenyl-3,4-dimethylenepyrroline) with DDQ or Pd/C in nitrobenzene gave in a cyclic aromatic amine polymer with repeating pyrrole rings in the polymer backbone. Using Pd/C in... 

K Ishihara, M Kobayashi, N Ishimaru, I Shinohara. Glucose induced permeation control of insulin through a complex membrane consisting of immobilized glucose oxidase and a poly(amine). Polym J 8 625-631, 1984. 

Mdleleni and coworkers137 anchored RhCl3 onto several porous aminated polymers. As displayed in Table 43, the best polymer support was found to be poly (4-vinylpyridine). Conditions T = 100 °C Pco = 0.9 atm RhCl3 3H20 = 5 x 10 5 mol solvent/H20 = 4/1 v/v. 

Imanaka—heterogenization of Rh complexes. In 1991, Imanaka and coworkers124 reported the heterogenization of Rh complexes by binding them to aminated polymers. As discussed previously, these findings led to fruitful research by Ford, Pardey, and others. The isolated polymer-bound Rh carbonyl anion complex was found to be reusable for reactions such as water-gas shift and reduction of nitro compounds. The polymer-bound Rh complexes were characterized by infrared spectroscopy. Water-gas shift activity (80 mol H2 per mol Rh6(CO)i6 in 24 hours) was recorded using the Rh complexes at 100 °C with 0.92 atm of CO, 2.16 ml H20, 0.05 mmol Rh6(CO)16, aminated polystyrene, 5.0 mmol of N, 5.56 ml ethoxyethanol and reduction of nitro-compounds (e.g., aliphatic nitro compounds to nitriles, oximes to nitriles, hydroxylamines to nitriles, and N-oxides to amines) occurred at 40 °C. 

Gao, Y., Robertson, G. R, Guiver, M. D., Jian, X. G., Mikhailenko, S. D. and Kaliaguine, S. 2005. Proton exchange membranes based on sulfonated poly(phthalazinone ether ketone)s/aminated polymer blends. Solid State Ionics 176 409-415. 

Polymeric polyamines are also strongly adsorbed in the compact region of the electric double layer as a combination of multisite electrostatic and hydrophobic interactions. The adsorption results in masking the silanol groups and the other adsorption active sites on the capillary wall and in altering the EOF, which is lowered and in most cases reversed from cathodic to anodic. One of the most widely employed polyamine coating agents is polybrene (or hexadimetrine bromide), a linear hydrophobic polyquaternary amine polymer of the ionene type [129]. 

The palladium-catalyzed amination reaction with a monofunctional primary amine 167 effects i / -diarylation to afford the tertiary amine polymers 168. Hence, polycondensation of 167 with bifunctional arylene dihalides leads to 168 (Equation (81)). Polycondensation of a primary amine bearing an azobenzene moiety with dibromides in the presence of Pd2(dba)3 (2.5mol%)- Bu3P (P/Pd = 3 l) and NaO Bu at 100°G for 24h in toluene gives 168 in 81-93% yields, as reported by Kanbara. 

We have found that the primary amine moiety can be protected from organolithium reagents and polymers by use of the N,N-bis(trimethylsilyl)amine, -N(TMS)p, protecting group. In turn, the N(TMS)2 substituted4 polymers can be converted to primary amine polymers by simple hydrolysis (Eqs. 12-14 (14.52). 

Aryl amine polymers were prepared by Sagisaka et al. (3) and Okada et al. (4),... 

Other work (I) has shown that the reaction of titanium(IV) chloride and trimethylamine yielded a mixture which was 90% tetrachloro( trimethylamine)-titanium(IV) and 10% trichlorobis (trimethylamine) titanium (III). The oxidation product of the reaction was not identified. However, the authors suggested that the oxidation products could be amine polymers or chloroamine derivatives. 

Low-molecular-weight model compounds such as phenylglycidyl or other mono-glycidyl ethers as well as primary, secondary and tertiary amines have been used for the study of the kinetics, thermodynamics and mechanism of curing. To reveal the kinetic features of network formation, results of studies of the real epoxy-amine systems have also been considered. Another problem under discussion is the effect of the kinetic peculiarities of formation of the epoxy-amine polymers on their structure and properties. 

Fig. la and b. IR-spectra of epoxy-amine polymers and model compounds at 298 K 36 a. 1 linear polymer VIII (see Table 3), 2-4 stoichiometric networks based on diglycidyl ether of resorcinol and m-phenylenediamine (2) and 4,4 -diaminodiphenylsulfone (3) and diglycidyl ether of hydroquinone and m-phenylenediamine (4). b. Model compounds II, III, VI (Table 3), (a) crystal (b) melt (c) glass... 

Rhodium(II) acetate catalyzes C—H insertion, olefin addition, heteroatom-H insertion, and ylide formation of a-diazocarbonyls via a rhodium carbenoid species (144—147). Intramolecular cyclopentane formation via C—H insertion occurs with retention of stereochemistry (143). Chiral rhodium (TT) carboxamides catalyze enantioselective cyclopropanation and intramolecular C—N insertions of CC-diazoketones (148). Other reactions catalyzed by rhodium complexes include double-bond migration (140), hydrogenation of aromatic aldehydes and ketones to hydrocarbons (150), homologation of esters (151), carbonylation of formaldehyde (152) and amines (140), reductive carbonylation of dimethyl ether or methyl acetate to 1,1-diacetoxy ethane (153), decarbonylation of aldehydes (140), water gas shift reaction (69,154), C—C skeletal rearrangements (132,140), oxidation of olefins to ketones (155) and aldehydes (156), and oxidation of substituted anthracenes to anthraquinones (157). Rhodium-catalyzed hydrosilation of olefins, alkynes, carbonyls, alcohols, and imines is facile and may also be accomplished enantioselectively (140). Rhodium complexes are moderately active alkene and alkyne polymerization catalysts (140). In some cases polymer-supported versions of homogeneous rhodium catalysts have improved activity, compared to their homogenous counterparts. This is the case for the conversion of alkenes direcdy to alcohols under oxo conditions by rhodium—amine polymer catalysts... 

The amine polymers used to prepare glucose sensitive polymers are heterogeneous. The rate of response is slow because of the slow rate of amine transfer from a hydrophobic phase to the aqueous phase. 

The method of synthesis20-25 consists in the preparation by anionic polymerization of a monodisperse first block, followed by chemical modification of its living end in order to introduce a terminal primary amine function into the molecule this to aminated polymer is then used as a macromolecular initiator for the polymerization of the N-carboxy anhydride (NCA) of the desired amino add. 

From the carboxylated polymer (PV—COOH) one obtains an aminated polymer (PV—NH2) by two different ways ... 

The calculated equilibrium network moduli of elasticity and experimental moduli measured in the rubbery state10,34) of different epoxy-amine networks show quantitative agreement. This means that the real structural nonuniformity of cross-linked epoxy-aromatic amine polymers exists only at the level of statistical deviations of network structure from the ideal one. A comparison of Ecalc and E p is shown in Fig. 4. 

Therefore, the increase in the crosslink density itself at the latest stages of the cure process cannot markedly increase the mechanical (cry, E) properties of glassy epoxyaromatic amine polymers. 

Post-cure thermal treatment of epoxy-aromatic amine polymers stabilizes mechanical properties to a certain extent. However, the embrittlement makes the treatment harmful from the point of view of engineering material properties. 

Studies of epoxy-amine polymers, considered in the present article, offer a rather clear picture of structure-properties relationships for many properties of network polymers depending on their chemical composition in the glassy state near Tg and in the rubbery state. Mechanical properties in the rubbery state at a given chemical composition depend on network topology. 

From carbodiimides The aminated polymers (from haloalkylpoystyrenes and potassium phtalimide) were converted into urea with isocyanate and dehydrated to carbodiimides 20 addition of tetramethylguanidine gave the type 5 N-hexalkylbiguanides 9 (Figure 14). 

Angeloni, A. S Ferruti, P and Laos, M Mannich bases in polymer synthe.sis. 7, lY)ly(N-aminomeihyleneamides) by polycon-densalion reaction of bis Mannich bases of dicarboxyamides with bis secondary amines. Polymer Common., 25, 119, 1984. 

The facile way by which zeolitic frameworks can be formed is further confirmed by their production imder acid and nonaqueous conditions, from the gas phase, and with organic additives as diverse as simple alcohols and amines, polymers, crown ethers, and dye molecules. 

In addition to the above mentioned, there have been reports of other polymers deposited using CVP, but extensive studies have not been done. Reports on 4-fluorostyrenes, ° polypyrrole and epoxy-amine polymers can be foundelsewhere, and are not discussed in detail in this paper. 

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