Poly(lactic acid) crystallization

Epitaxial crystallization of polymers on organic and polymeric substrates

An overview of the literature together with selected authors' data on thermal and thermo-oxidative decomposition of commercial aliphatic nylons (nylon 6, nylon 7, nylon 11, nylon 12, nylon 6.6, nylon 6.10, nylon 6.12) is presented. Despite the high level of research activity and the large number of publications in the field, there is no generally accepted mechanism for the thermal decomposition of aliphatic nylons. Polylactams (nylon 6, nylon 11 and nylon 12) tend to re-equilibrate to monomeric or oligomeric cyclic products. Diacid–diamine type nylons (nylon 6.6, nylon 6.10 and nylon 6.12) produce mostly linear or cyclic oligomeric fragments and monomeric units. Because of the tendency of adipic acid to fragment with elimination of CO and H2O and to undergo cyclization, significant amounts of secondary products from nylon 6.6 are reported in some papers.

 Many authors have shown that the primary polyamide chain scission occurs either at the peptide C(O)NH or at adjacent bonds, most probably at the alkyl–amide NHCH2 bond which is relatively the weakest in the aliphatic chain. Hydrolysis, homolytic scission, intramolecular CH transfer and cis-elimination (a particular case of CH transfer) are all suggested as possible primary chain-scission mechanisms. There are no convincing results reported which tend to generally support one of these mechanisms relative to the others; rather, it seems that the contribution of each mechanism depends on experimental conditions. This conclusion is also supported by the wide spread of kinetic parameters measured under the different experimental conditions.

 More uniform results are observed in the literature regarding the mechanism of thermo-oxidative decomposition of aliphatic nylons. Most authors agree that oxygen first attacks the N-vicinal methylene group, which is followed by the scission of alkyl–amide NC or vicinal CC bond. Alternatively, it is suggested that any methylene group which is β-positioned to the amide group methylene can be initially oxidized. There are few mechanisms in the literature which explain discoloration (yellowing) of nylons. UV/visible active chromophores are attributed either to pyrrole type structures, to conjugated acylamides or to conjugated azomethines.

 Some secondary reactions occurring during the thermal or thermo-oxidative decomposition lead to crosslinking of nylons. Nylon 6.6 crosslinks relatively easily, especially in the presence of air, whereas nylon 11 and nylon 12 crosslink very little. Strong mineral acids, strong bases, and some oxides or salts of transition metals catalyse the thermal decomposition of nylons, but minimize crosslinking. In contrast, many fire retardant additives promote secondary reactions, crosslinking and charring of aliphatic nylons.

© 1999 Society of Chemical Industry

Thermal decomposition of aliphatic nylons

Compatibility and transesterification in binary polymer blends

Preface. Acknowledgments. Contributors. PART 1. An Environmental Primer (A. Andrady). Common Plastics Materials (A. Andrady). Polymers and Energy (I. Boustead) PART 2. Plastics in Packaging (S. Selke) Plastics in Agriculture (I. Hussain & H. Hamid). Coatings (L. Hill). Wastes From Textiles Processing (B. Smith). PART 3. Environmental Effects on Polymeric Materials (N. Searle). Biodegradable Polymers (S. McCarthy). Plastics in the Marine Environment (M. Gregory and A. Andrady). Flammability of Polymers (A. Tewarson). Biodegradable Water-Soluble Polymers (G. Swift). PART 4. Polymers, Polymer Recycling, and Sustainability (J. Brandrup). Plastics Recycling (M. Fisher). Thermal Destruction of Wastes and Plastics (A. Gupta & D. Lilley). Recycling of Carpet and Textile Fibers (Y. Wang, et al.). Polymers in Automobile Applications (W. Lange). Index.

Plastics and the environment

This paper is devoted to the study of the reactions taking place in molten bisphenol-A polycarbonate-poly(ethylene terephthalate) mixtures. The analysis of the reaction products by infrared, proton and nuclear magnetic resonance spectroscopy, and by thermogravimetric analysis shows that the main reaction is an exchange reaction identical to that occurring in bisphenol-A polycarbonate-poly(butylene terephthalate) mixtures. However, some other reactions consecutive to this exchange reaction also take place, probably resulting from the instability of the ethylene carbonates produced by transesterification.

Molten bisphenol‐A polycarbonate‐poly(ethylene terephthalate) blends. I. Identification of the reactions

Chemical nucleation, a new concept applied to the mechanism of action of organic acid salts on the crystallization of polyethylene terephthalate and bisphenol—A polycarbonate

Jm. Dekoninck

Papers

Molten bisphenol‐A polycarbonate‐poly(ethylene terephthalate) blends. I. Identification of the reactions

Chemical nucleation, a new concept applied to the mechanism of action of organic acid salts on the crystallization of polyethylene terephthalate and bisphenol—A polycarbonate

Molten bisphenol‐A polycarbonate—poly(ethylene terephthalate) blends. II. Kinetics of the exchange reaction.

Crystallization of poly(ethylene terephthalate) induced by organic salts: model compound study of the mechanism of action of the nucleating agent

Nucleation of Poly(ethylene-terephthalate) By Sodium Compounds - a Unique Mechanism