Poly derivatives synthesis

S. Ramakrishnan and T.C. Chung, Poly(5-hydroxyoctenylene) and its derivatives Synthesis via metathesis polymerization of an organobor-ane monomer, Macromolecules, 23(21 ) 4519-24,1990. 

Rajca, S., Rajca, A., Wongsriratanakul, J., Butler, P. and Choi, S. (2004). Organic spin clusters. Dendritic-macrocyclic poly ary lmethyl polyradical with very high-spin of 5=10 and its derivatives synthesis, magnetic studies, and small angle neutron scattering. J. Am. Chem. Soc. 126, 6972-6986... 

Ganesh SD, Pai VK, Kariduraganavar MY, Jay anna MB. Fluorinated poly(arylene ether-1,3,4-oxadiazole)s containing a 4-bro-mophenyl pendant group and its phosphonated derivatives synthesis, spectroscopic characterization, thermal and dielectric studies. Polym-Plastics Technol Eng 2013. 

Various polymerization route with unique starting monomer [64] have been developed, e.g., topochemical poly(diacetylene) synthesis with pyrrole-, thiophene-, -Si-groups dienophilic addition of maleic imides, Diels-Alder polymers via cyclopentadienone derivatives. 

Feng, J., Zhang, Q., Li, W., Li, Y., Yang, M., Cao, Y.J. Novel porph5uin-grafted poly (phenylene vinylene) derivatives Synthesis and photovoltaic properties. Appl. Polym. Sci. 109, 2283-2290 (2008)... 

It has also been found that polymers possessing functional groups such as amines and pyridines are soluble in pregeUed sol solutions, especially, poly(2-vin5ipyridine) and poly(N-vinylpyrroHdinone) (PVP) (49). There, materials were made as part of a study of the synthesis of nonshrinking sol—gel-derived networks (49). 

In another process for the synthesis of PPS, as well as other poly(arylene sulfide)s and poly(arylene oxide)s, a pentamethylcyclopentadienylmthenium(I) TT-complex is used to activate -dichlorobenzene toward displacement by a variety of nucleophilic comonomers (92). Important facets of this approach, which allow the polymerization to proceed under mild conditions, are the tremendous activation afforded by the TT-coordinated transition-metal group and the improved solubiUty of the resultant organometaUic derivative of PPS. Decomplexation of the organometaUic derivative polymers may, however, be compHcated by precipitation of the polymer after partial decomplexation. 

Alkylated phenol derivatives are used as raw materials for the production of resins, novolaks (alcohol-soluble resins of the phenol—formaldehyde type), herbicides, insecticides, antioxidants, and other chemicals. The synthesis of 2,6-xylenol [576-26-1] h.a.s become commercially important since PPO resin, poly(2,6-dimethyl phenylene oxide), an engineering thermoplastic, was developed (114,115). The demand for (9-cresol and 2,6-xylenol (2,6-dimethylphenol) increased further in the 1980s along with the growing use of epoxy cresol novolak (ECN) in the electronics industries and poly(phenylene ether) resin in the automobile industries. The ECN is derived from o-cresol, and poly(phenylene ether) resin is derived from 2,6-xylenol. 

The condensation of a vinylogous formamide with an enamine has been applied to an aza azulene synthesis (351). The point of attachment of the aldehyde to the enamine in condensations with indolenin derived poly-enamines was found to favor the second double bond (352,353). 

Poly(L-malic acid) denotes a family of polyesters derived from L-malic acid as the building unit. By chemical synthesis, three kinds of poly(L-malic acid) have been obtained, depending on the molecular position of the ester bond the a-type(I) [1], the j8-type(II) [2], and the a,j8-mixed-type(III) [3). 

There have been very few examples of PTV derivatives substituted at the vinylene position. One example poly(2,5-thienylene-1,2-dimethoxy-ethenylene) 102 has been documented by Geise and co-workers and its synthesis is outlined in Scheme 1-32 [133]. Thiophene-2,5-dicarboxaldehyde 99 is polymerized using a benzoin condensation the polyacyloin precursor 100 was treated with base to obtain polydianion 101. Subsequent treatment with dimethyl sulfate affords 102, which is soluble in solvents such as chloroform, methanol, and DMF. The molar mass of the polymer obtained is rather low (M = 1010) and its band gap ( ,.=2.13 eV) is substantially blue-shifted relative to PTV itself. Despite the low effective conjugation, the material is reasonably conductive when doped with l2 (cr=0.4 S cm 1). 

One of the first examples was the above mentioned work from Yoshino et al. [7] concerning the synthesis of poly(9,9-dialkylfluorene)s via oxidative coupling of fluorene derivatives. Poly(9,9-dialkylfluorene) derivatives have been also synthesized via Ni- and Pd-catalyzed aryl-aryl homo- and cross-coupling reactions of sui-... 

There have been a number of different synthetic approaches to substituted PTV derivatives proposed in the last decade. Almost all focus on the aromatic ring as the site for substitution. Some effort has been made to apply the traditional base-catalyzed dehydrohalogenation route to PTV and its substituted analogs. The methodology, however, is not as successful for PTV as it is for PPV and its derivatives because of the great tendency for the poly(u-chloro thiophene) precursor spontaneously to eliminate at room temperature. Swager and co-workers attempted this route to synthesize a PTV derivative substituted with a crown ether with potential applications as a sensory material (Scheme 1-26) [123]. The synthesis employs a Fager condensation [124] in its initial step to yield diol 78. Treatment with a ditosylate yields a crown ether-functionalized thiophene diester 79. This may be elaborated to dichloride 81, but pure material could not be isolated and the dichloride monomer had to be polymerized in situ. The polymer isolated... 

Ebdon and coworkers22 "232 have reported telechelic synthesis by a process that involves copolymerizing butadiene or acetylene derivatives to form polymers with internal unsaturation. Ozonolysis of these polymers yields di-end functional polymers. The a,o>dicarboxy1ic acid telechelic was prepared from poly(S-s tot-B) (Scheme 7.19). Precautions were necessary to stop degradation of the PS chains during ozonolysis. 28 The presence of pendant carboxylic acid groups, formed by ozonolysis of 1,2-diene units, was not reported. 

Poly(arylene thioether)s, 363-364 Poly(arylene thioether sulfone)s, 364 Poly(aryl sulfone) derivatives, 354 Poly(p-benzamide), synthesis of, 188-189 Polybenzimidazoles (PBIs), 265 ferrocene-containing, 315 synthesis of, 313... 

Polymers like those in the poly aniline family interchange protons and anions with the solution, allowing a local modulation of pH. Composites that interchange cations allow the modulation of any cation concentration. Efforts are being devoted to the synthesis of polymer or polymeric derivatives having great cationic specificity. 

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