Poly thermal decomposition

SolubiHty parameters of 19.3, 16.2, and 16.2 (f /cm ) (7.9 (cal/cm ) ) have been determined for polyoxetane, po1y(3,3-dimethyl oxetane), and poly(3,3-diethyloxetane), respectively, by measuring solution viscosities (302). Heat capacities have been determined for POX and compared to those of other polyethers and polyethylene (303,304). The thermal decomposition behavior of poly[3,3-bis(ethoxymethyl)oxetane] has been examined (305). 

Several substituted linear polyphenylenes have also been prepared but none appear to have the resistance to thermal decomposition shown by the simple poly-p-phenylene. 

The phosphazene backbone has a particularly high resistance to thermal treatment and to homolytic scission of the -P=N- bonds, possibly due to the combination of the high strength of the phosphazene bond and its remarkable ionic character [456]. As a consequence, the onset of thermal decomposition phenomena (as detected, for instance, by TGA) are observed at considerably high temperatures for poly[bis(trifluoroethoxy)phosphazene], [NP(OCH2CF3)2]n [391, 399, 457], for phosphazene copolymers substituted with fluorinated alcohols of different length [391, 399, 457], for polyspirophosphazenes substituted with 2,2 -dihydroxybiphenyl groups [458], and for poly(alkyl/aryl)-phosphazenes [332]. 

The thermal properties of tyrosine-derived poly(iminocarbonates) were also investigated. Based on analysis by DSC and thermogravi-metric analysis, all poly(iminocarbonates) decompose between 140 and 220 C. The thermal decomposition is due to the inherent instability of the iminocarbonate bond above 150°C and is not related to the presence of tyrosine derivatives in the polymer backbone. The molecular structure of the monomer has no significant influence on the degradation temperature as indicated by the fact that poly(BPA.-iminocarbonate) also decomposed at about 170 C, while the structurally analogous poly(BPA-carbonate) is thermally stable up to 350 C. 

The low thermal stability of many poly(iminocarbonates) limits the use of melt fabrication techniques such as injection molding or extrusion. For example, among all six polymers tested, only poly-(Dat-Tyr-Hex) and poly(CTTH) had low enough softening points to be compression moldable without a significant degree of thermal decomposition. ... 

The unbranched polymer produced by P. polycephalum and related Physarum strains has a weight average molecular weight between 40,000 and 60,000 Daltons and a polydispersity of 1.5-3.0 depending on the culture conditions and the age of the samples [111]. The acid form of poly-/ -malate does not show either a Tg or a Tm in the solid state, by DSC analysis, below its thermal decomposition temperature of 185 °C. 

The FTIR spectra of the gas mixture evolved in thermal decomposition of Bisphenol AF poly(formal) (7) at various temperatures suggest the existence of benzene rings, C—O—C bonds, and C=C bonds. In a pyrogram of pyrolysis gas chromatography (Py-GC) of Bisphenol A (3), a-methylstyrene, phenol, p-cresol, 4-hydroxy-amethylstyrene, and isopropyl phenol are observed as major peak products. The cleavage reactions shown in Scheme (5) is suggested for the formation of phenol and 4-hydroxy-a-methylstyrene from Bisphenol A (3). 

At the other end of the temperature spectrum, with high thermal stability of siloxane-modified poly(arylene carbonates) also a desired property, the onset of thermal decomposition (40) for polymers 1-12 was found to be in the range of 385-456°C (as determined from TGA curves obtained by heating polymer samples in nitrogen at a heating rate of 20°C/min.). There does not appear to be any pronounced trend in regard to variation of the thermal stability with structure in polymers 1-12. The small differences in the values of T for these polymers can be due... 

Li XH, Meng YZ, Zhu Q, Tjong SC (2003) Thermal decomposition characteristics of poly (propylene carbonate) using TG/fR and Py-GC/MS techniques. Polym Degrad Stab 81 157-165... 

In the presence of a dissolved polymer, the radical polymerization of a monomer by thermal decomposition of an initiator results in a mixture of homopolymerization and graft polymerization [Brydon et al., 1973, 1974 Ludwico and Rosen, 1975, 1976 Pham et al., 2000 Russell, 2002], Polymer radicals (XXX), formed by chain transfer between the propagating radical and polymer, initiate graft polymerization of styrene. The product (XXXI) consists of polystyrene grafts on the 1,4-poly-1,3-butadiene backbone. Polymer radicals are also formed... 

Platonova et al. reported a preparation method of Co nanoparticles having good dispersibility using block copolymer (polystyrene poly-4-vinyl piridine) mi-cells where Co was generated by the reduction of micells loaded with CoCl2 and by thermal decomposition of Co2(CO)s in micellar solutions of the block copolymers... 

Thus, N-pyrimidine phthalimide reacted with hexylamine at room temperature to form an amide-amide. The initial amide-amide formation proceeded more rapidly in chloroform as compared to dimethylsulfoxide (DM SO). However, the ring closure reaction to the imide was favored by the more polar, aprotic DMSO solvent, yielding the imide in nearly quantitative yield after 3 hours at 75 °C. The authors were able to utilize this synthetic approach to prepare well-defined segmented poly(imide-siloxane) block copolymers. It appears that transimidi-zation reactions are a viable approach to preparing polyimides, given that the final polyimide has a Tg sufficiently low to allow extended excursions above the Tg to facilitate reaction without thermal decomposition. Additionally, soluble polyimides can be readily prepared by this approach. Ultimately, high Tg, insoluble polyimides are still only accessable via traditional soluble precursor routes. 

The poly(ester-imides) are produced by the thermal decomposition of the soluble polytamic acids) which are obtained by the condensation of ail aromatic diamine and the bis-fester anhydride) of trimeUitic anhydride as shown in the following equation ... 

Zinc complexes are important as additives for rubber polymers. Dithiocarbamate complexes are most commonly used here, but bis(8-hydroxyquinolinato)zinc inhibits the thermal decomposition of poly[(trifluoroethoxy)(octafluoropentoxy)phosphazene]. The zinc is thought to complex residual P—OH groups in the polymer chain, which would otherwise lead to rearrangement and chain scission.126... 

Pyrolysis of poly(methylacetylene) shows rather similar behaviour 528>, with mesi-tylene as the major product but substantial yields of methyl and proton-enriched products. Thermal decomposition of this polymer sets in at around 150 °C and the mechanism is postulated to involve chain scission followed by cyclization reactions and both electron-proton and electron-methyl exchanges. Pyrolysis of poly(phenyl-acetylene) has been reported to start at 270 °C in nitrogen 529). 

The thermal and photochemical dehydrochlorination of the vinyl chloride—CO copolymer have been studied by two different groups56,57). The decomposition rate for the copolymer was significantly higher than that for poly(vinyl chloride), the rate increasing with increasing CO content of the copolymer. In addition, the thermal decomposition of the copolymer was accelerated in the presence of molecular 02 while the photodegradation was slowed down 57). As with poly(vinyl chloride), the dehydrochlorination of the copolymer resulted in the formation of polyene sequences. There was no appreciable decrease in molecular weight. 

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