Poly substituted polymers

Applications. Among the P—O- and P—N-substituted polymers, the fluoroalkoxy- and aryloxy-substituted polymers have so far shown the greatest commercial promise (14—16). Both poly[bis(2,2,2-trifluoroethoxy)phosphazene] [27290-40-0] and poly(diphenoxyphosphazene) [28212-48-8] are microcrystalline, thermoplastic polymers. However, when the substituent symmetry is dismpted with a randomly placed second substituent of different length, the polymers become amorphous and serve as good elastomers. Following initial development of the fluorophosphazene elastomers by the Firestone Tire and Rubber Co., both the fluoroalkoxy (EYPEL-F) and aryloxy (EYPEL-A) elastomers were manufactured by the Ethyl Corp. in the United States from the mid-1980s until 1993 (see ELASTOLffiRS,SYNTHETic-PHOSPHAZENEs). 

The chemical modification of poly (2,6-dimethyl-l,4-phenylene oxide) (PPO) by several polymer analogous reactions is presented. The chemical modification was accomplished by the electrophilic substitution reactions such as bromination, sulfonylation and acylation. The permeability to gases of the PPO and of the resulting modified polymers is discussed. Very good permeation properties to gases, better than for PPO were obtained for the modified structures. The thermal behavior of the substituted polymers resembled more or less the properties of the parent polymer while their solution behavior exhibited considerable differences. 

All of the soluble polymers (1 and 3-6) give high resolution NMR spectra (1H, 13C, and 31P) that are completely consistent with their proposed structures. As observed for other types of poly(phosphazenes), the 31P chemical shifts of these alkyl/aryl substituted polymers are consistently ca. 15-30 ppm upfield from those of the analogous cyclic trimers and tetramers. Some important structural information is provided by 13C NMR spectroscopy, particularly for the phenyl/alkyl derivatives 3 and 4. These polymers are rare examples of phos-phazenes that contain two different substituents at each phosphorus atom in the chain. Thus, they have the possibility of being stereoregular. The fact that the structures are completely atactic, however, is confirmed by the observation of three doublets in the P-Me region of the 13C NMR spectrum (ca. 22 ppm) in a 1 2 1 intensity ratio. 

Thermogravimetric analysis (TGA) of these poly(phosphazenes) shows their decomposition onset temperatures in an inert atmosphere to be ca. 350 to 400°C, depending on the side group. These temperatures are ca. 25-75°C higher than that reported for commercial materials based on the fluoroalkoxy substituted polymer, [(CFgCHjO PN],. (19) Interestingly, methyl rather than phenyl side groups yield the more stable materials, as shown by... 

Samples of the poly(dialkylphosphazenes) 1 and 2 displayed X-ray powder diffraction patterns characteristic of crystalline regions in the materials. The peaks in the diffraction pattern of 1 were of lower amplitude and greater angular breadth than those of 2. These data indicate that poly(diethylphosphazene) (2) is highly crystalline while poly(dimethyl-phosphazene) (1) is more amorphous with smaller crystalline zones. This high degree of crystallinity is probably responsible for the insolubility of 2 as noted above. All of the phenyl substituted polymers 3-6 were found to be quite amorphous in the X-ray diffraction studies, a result that is further evidence for an atactic structure of the poly(alkylphenylphosphazenes) 3 and 4 and for a random substitution pattern in the copolymers 5 and 6. 

The synthesis of luminescent organoboron quinolate polymers (21) (Fig. 15) via a three-step procedure starting from a silylated polystyrene has been communicated. The synthesis was initiated by the highly selective borylation of poly (4-trimethylsilylstyrene) (PS-Si), followed by the replacement of the bromine substituents in poly(4-dibromoborylstyrene) (PS-BBr) with substituted thienyl groups (R = H, 3-hexyl, 5-hexyl). In the final step, the 8-hydroxyquinolato moiety was introduced. The hexyl-substituted polymers efficiently emitted light at 513-514nm upon excitation at 395 nm.40... 

Jakle and Wagner have communicated the synthesis of bromo-substituted, boranediyl-bridged poly(ferrocenylene)s (40) (Fig. 28) by the reaction of Fc(BBr2)2 with three equivalents of HSiEt3. The polymer 40 was transformed into the corresponding mesityl-substituted polymer (40Mes) by treating its slurry in toluene with... 

While this work has focused on certain allylic and benzylic ether derivatives of poly(4-hydroxystyrene) it is possible to extend the concept to the corresponding t-butoxy substituted polymers although the preparation of such polymers is relatively more difficult than in the present case. 

Production of pol3rmers through poly-substitution or poly-condensation reactions would be expected to be a natural extension of simple PTC chemistry. To a large extent this is true, but as Percec has shown. Chapter 9, the ability to use two-phase systems for these reactions has enormously extended the chemist s ability to control the structure of the polymers produced. Kellman and co-workers (Chapter 11) have also extensively studied poly-substitution displacements on perfluorobenzene substrate to produce unique polymers. 

In 1961, Gewald and co-workers published the synthesis of poly-substituted thiophenes involving condensation of cyanoacetate and elemental sulphur with ketones or aldehydes in a three-component reaction (Scheme 5.9). Beyond their industrial use in dyes and conducting polymers, 2,5-substituted thiophenes have shown extensive potential in the pharmaceutical industry. Most published Gewald thiophene synthetic procedures require reaction times between 8 and 48 h for the condensation step. Hoener and... 

The conductivity of doped poly(3,4-dimethylpyrrole) is lOScm-1, while conductivities of poly(diphenylpyrrole) and of poly(A-methyl pyrrole) are both about 10 3 S cm-1, very much reduced from pyrrole and dimethylpyrrole. This is attributed by Street to non-planarity of the substituted polymers 393). 

In 1996, Gauglitz and coworkers coated surfaces with various amino-and carboxy-substituted polymers [198], The polymers tested were branched poly-(ethyleneimine), a,co-amino-functionalized PEG, chitosan, poly(acrylamide-co-acrylic acid) and an amino-modified dextran. The amino-substituted polymers were immobilized on glass by first immobilizing an aminosilane, followed by succinic anhydride/A-hydroxysuccinimide linker chemistry. Poly(acrylamide-co-acrylic acid) was directly coupled to an aminosilanized surface. When probed with 1 mg mL 1 ovalbumin solution, nonspecific adsorption was lowest for the dextran derivative. Notably, nonspecific adsorption increased in most cases when a hydrophobic hapten (atrazine) was coupled to the polymer-modified surface. 

Pigment and filters Poly substituted phenol ethoxylates Phosphate esters Short chain amine EO/PO co-polymers Lignin sulphonates Wetters and dispersants... 

For halogen or alkoxy-substituted polymers Tg values are low (between -60 and —100° C). Alkoxy poly phosphazene with Ci - C3 substituents are elastomers. Higher alkoxy- or aryloxy-substituted polyphosphazenes are thermoplastics. Fluoroalkoxypolyphosphazenes exhibit a good stability toward diluted acids and bases. Some of them have outstanding thermal stability and good flame-retardant properties. 

Fluoro-substituted Polymers. The fluoropolymers were between the first to be studied by the XPS technique because the substitution of F atom(s) in the -CH.-CH - unit induced very large modifications in the XPS core level spectra (shifts up to 8eV) that were easy to detect and interpret. The XPS valence band spectra of similar compounds, namely poly(vinyl fluoride) (PVF), poly(vinylidene fluoride) (PVF2), poly(trifluoroethylene) (PVF3), and poly(tetrafluoroethylene) (PTFE) (26, 27, 28) are also expected to reflect the induction of such strong electronic effects at the valence molecular level. 

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