Extension of the chain‐end,free‐volume theory for predicting glass temperature as a function of conversion in hyperbranched polymers obtained through one‐pot approaches

Compared with linear polymers, more factors may affect the glass‐transition temperature (T_g) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. T_g's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of T_g to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. T_g's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. T_g values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. T_g values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of T_g versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that T_g increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004     

Gas-phase thermal decomposition of peroxy-N-butyryl nitrate

The gas-phase thermal decomposition rate of peroxy-n-butyryl nitrate (n-C₃H₇C(O)OONO₂, PnBN) has been measured at ambient temperature (296 K) and 1 atm of air relative to that of peroxyacetyl nitrate (CH₃C(O)OONO₂, PAN) using mixtures of PAN (14–19 ppb), PnBN (22–46 ppb), and nitric oxide (1.35–1.90 ppm). The PnBN/PAN decomposition rate ratio was 0.773 ± 0.030. This ratio, together with a literature value of 3.0 × 10^?4 s^?1 for the thermal decomposition rate of PAN at 296 K, yields a PnBN thermal decomposition rate of (2.32 ± 0.09) × 10^?4 s^?1. The results are briefly discussed by comparison with data for other peroxyacyl nitrates and with respect to the atmospheric persistence of PnBN. © 1994 John Wiley & Sons, Inc.     

Effect of reaction conditions on the molecular weight and polydispersity of linear poly(arylene ether phosphine oxide)s prepared from an AB monomer

A thorough study of the polymerization behavior of 4‐fluoro‐4′‐hydroxytriphenyl‐phosphine oxide, 2 , under nucleophilic aromatic substitution reactions has been carried out. The synthesis of 2 was achieved in excellent yields by the reaction of bis(4‐fluorophenyl)phenylphosphine oxide, 1 , with one equivalent of potassium hydroxide in DMSO/water. The structure and purity of 2 were confirmed via ¹H, ¹³C, and ³¹P NMR spectroscopy along with elemental analysis. Polymerization reactions of 2 in NMP or DMSO at 180 °C provided the corresponding linear poly(arylene ether phosphine oxide)s, PAEPOs, with number average molecular weights, M_n, ranging from 11,700 to 36,500 Da. All of the polymer samples were completely soluble in chloroform, tetrahydrofuran, DMSO, NMP, and DMAc. The polymerization reactions were accompanied by a competing intramolecular process that resulted in the formation of cyclic oligomeric species that were removed via a final precipitation from methanol. Analysis using ³¹P NMR spectroscopy and size exclusion chromatography (SEC) confirmed that the majority of the lower molecular weight cyclic species were removed via this process. The polymer samples formed tough films when chloroform solutions were slowly evaporated on a glass slide. The PAEPO samples prepared in this study exhibited excellent thermal stability with T_d (5%) values between 503 and 542 in air while the glass transition temperatures ranged from 223 to 237 °C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2099–2106, 2006     

Reaktionen von π-Organokomplexen des Nickels mit tertiären Phosphanen

Reactions of π-Organonickel Complexes with Tertiary Phosphanes In a hexane solution Ni(C₅H₅)₂ reacts with PBu₃ or Ph₂PBu forming the nickel(O) complexes Ni(PBu3)₄ or Ni(Ph₂PBu)₄ (A). Under the same conditions only one cyclopentadienyl ligand is substituted by PhPBu₂ and the nickel(I) compound (C₅H₅)Ni (PhPBu₂)₂ (B) is obtained. Products of the reactions between B and α,α′-dipyridyl, hydrogen chlorid in ether, or Ni(PhPBu₂),Cl₂ are Ni(dipy)₂, [PhPHBu₂]₂[NiCl₄], or (C₅H₅) Ni(PhPBu₂)₂Cl. By the reaction with HgCl₂ a cyclopentadienyl compound of an unknown structur is formed. The compound Ni(PhPBu₂)₄ which is analogous to A is synthesized by the reduction of bis(acety1acetonato)-nickel with Et₂AlOEt in the presence of PhPBu₂ or by the reaction of bis (cyclooctadiene-1,5)-nickel with PhPBu₂.     

Die Massenspektren der Pyrrolidide einiger aliphatisch-alicyclischer Carbonsäuren

The mass spectra of the pyrrolidides of some long-chain carboxylic acids with alicyclic residues attached to their ω-end are discussed and compared with the spectra of the corresponding esters. Fragmentation triggered by the pyrrolidide group generates a series of peaks, which clearly exhibits the size and the structure of the carbon chain.     

Reactions of 6-diazopenicillanates with allylic sulphides,selenides, and bromides

6-Diazopenicillanates react with allylic sulphides, selenides and bromides, to give 6,6-disubstituted penicillanates $\text{via}$ [2,3]-sigmatropic rearrangements.