The mechanisms of the Michael addition polymerizations of different trifunctional amines with an equimolar 1,4-butanediol diacrylate (BDA) were investigated by using 1H and 13C NMR to in situ monitor the polymerization processes. The trifunctional amine monomers adopted were 1-(2-aminoethyl)piperazine (AEPZ) and 4-(aminomethyl)piperidine (AMPD) and linear aliphatic amines with different steric hindrance on the 2° amines (original), i.e., N-methylethylenediamine (MEDA), N-ethylethylenediamine (EEDA), and N-hexylethylenediamine (HEDA). For AEPZ, AMPD, and MEDA with low steric hindrance on the 2° amines (original), the reactivity sequence of the three types of amines was 2° amines (original) > 1° amines ≫ 2° amines (formed) and linear poly(amino ester)s were formed via AB-type intermediates due to the 2° amines (formed) being kept out of the reaction. However, AB-type intermediates were only formed from the 2° amines (original) for AEPZ and AMPD, but from both the 2° amines (original) and 1° amines due to their smaller reactivity difference for MEDA. Nevertheless for EEDA and HEDA, the increased steric hindrance on the 2° amines (original) changed the reactivity sequence of the three types of amines to 1° amines > 2° amines (original) > 2° amines (formed) and branched polymers with degrees of branching of ca. 33% and 37%, respectively, were obtained due to all the three types of amines participating in the reaction. The molecular weights, glass transition temperatures, and thermal stability of the linear or branched poly(amino ester)s obtained were characterized by GPC, DSC, and TGA, respectively.
Crude palm oil contains about 1% of minor components including carotenoids, tocopherols, sterols, triterpene alcohols, phospholipids, glycolipids and terpenic and paraffinic hydrocarbons. The nutritionally important components such as carotenes and tocopherols also improve stability of the oil. Although a highly valued product, carotene unfortunately is bleached or destroyed in refining because suitable recovery technology is not available. Thermal degradation of carotene, previously suspected of giving rise to undesirable chemicals, now is known to furnish mainly harmless hydrocarbons, most of which are removed by the deodorization step in refining. Tocopherols, being natural antioxidants, need to be carefully preserved during milling, refining, fractionation and modification of palm oils. The accumulation of tocopherols in the palm fatty acid distillate promises to provide a new source for the recovery of this valuable substance. The role played by phospholipids is frequently misunderstood because they can act in two ways, i.e. as an antioxidant synergist and a surface active agent to disperse impurities in oil. In crude palm oil the phospholipid content is small, because most of it is removed during milling; the phosphorus content is due mainly to inorganic phosphorus. Among the sterols, cholesterol constitutes too small a percentage to be of much concern. Sterols, triterpenoids and terpenoid hydrocarbons are also potentially useful side products should recovery technology become available. Other newly characterized minor and trace components also are discussed.
The kinetics for the epoxidation of methyl esters of palm olein (MEPOL) by peroxyformic acid and peroxyacetic acid generated in situ were studied. The rate-determining step was found to be the formation of peroxy acid. Epoxidized MEPOL (EpMEPOL), with almost complete conversion of the unsaturated carbon and negligible ringopening, can be synthesized by the in situ technique described.The kinetics of the oxirane cleavage of EpMEPOL by acetic acid were studied at various temperatures. The reaction was found to be first-order with respect to the epoxy concentration and second-order to the acetic acid concentration. The activation energy and the entropy of activation for the epoxidation of MEPOL were comparable to those for the oxirane cleavage of EpMEPOL by acetic acid, suggesting that the two reactions are competitive. The success of the epoxidation of MEPOL with only negligible oxirane cleavage is attributed to the heterogeneous nature of the system employed in the in situ technique.
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