Characterization of the Microstructure of Bimodal HDPE Resin

In this work, two industrial bimodal high density polyethylene resins, resin A and resin B having similar molecular weight (M-w), molecular weight distribution (M-wD), and short-chain branching (SCB) content but different mechanical properties, were fractionated through cross-fractionation. The fractions were further, characterized by GPC, C-13 NMR, DSC AND FT IR techniques. These two resins were firstly fractionated into two franctions, i.e. high-temperature and low temperature fractions, via preparative solution crystallization fractionation. Resin A with much better mechanical properties contains more high-temperature fractions with longer crystalizable sequences. The SCB content in the low temperature fraction of resin A is lower than the of resin B. Both low-temperature fractions were then further fractionated using solvent gradient fractionation (SGF). The characterization of SGF fraction indicates that most of the branches fall into the high molecular weight chain in both low-temperature fractions.

Solvent effects on spectrophotometric titrations and vibrational spectroscopy of 5,10,15-triphenyl-20-(4-hydroxyphenyl)porphyrin in aqueoius DMF

The spectrophotometric titration by sodium hydroxide of 5,10,15-triphenyl-20-(4-hydroxyphenyl)porphyrin ((OH)(1)PH2) is studied as a function of solvent composition of DMF-H2O binary solvent mixture ([OH-] = 0.04 M). Combining the structure changes of the porphyrin and the "four orbital" model of Gouterman, many features of the optical spectra of this deprotonated para-hydroxy-substituted tetraphenylporphyrin in different composition of binary solvent mixtures can be rationalized. In highly aqueous solvents, the changes of the titration curves are shown to be mainly due to hydrogen-bonding of the oxygen of the phenoxide anion group by the hydroxylic solvent, Which decreases the energy of the phenoxide anion pi orbital. Thus the phenoxide anion pi orbital cannot cross over the porphyrin Tr orbital being a different HOMO. However, its energy is close to that of the porphyrin pi orbitals. As a result, in the visible region, no charge-transfer band is observed, while in the visible-near region, the Soret peak split into two components. In nonaqueous solvents, the changes are mainly attributed to further deprotonation of pyrrolic-Hs of (OH) 1PH2 by NaOH and coordination with two sodium ions to form the sodium complex of (OH) 1PH2, which turns hyperporphyrin spectra of deprotonated of phenolic-H of (OH)(1)PH2 into three-banded spectra of regular metalloporphyrin.