Epoxide polymers mechanisms

The mechanism, developed by Penczek, in the presence of an excess of hydroxyl groups, is very similar to a solvolysis reaction [55] and is characterised by the presence of the active cationic centre to the monomer in the form of a secondary oxonium cation. The polymer chain extension takes place by the SN2 reaction of hydroxyl groups with the activated epoxide. This mechanism is called activated monomer mechanism (AM mechanism), characterised by the relationship [OH] [PO] (reaction 7.21). 

Vandenberg, E.J., 1969. Epoxide polymers synthesis stereochemistry structure and mechanism. J. Polym. Sci. Part A Polym. Chem. 7 (2), 525-567. 

In Table 3 some physical-mechanical and dielectric properties of modified and unmodified epoxide polymers are presented. From the data resulted in Table 3 it is visible, that by using of epoxy siliconotganic compounds I and II, as active thinners of epoxy compositions, their strength properties and dielectric parameters practically do not undergo essential changes. 

Vandenberg, E. J. Epoxide polymers Synthesis, stereochemistry, structure, and mechanism. J. Poly. Sci., Poly. Chem. Ed. 1969, 7, 525-567. 

These monomers provide a means for introducing carboxyl groups into copolymers. In copolymers these acids can improve adhesion properties, improve freeze-thaw and mechanical stability of polymer dispersions, provide stability in alkalies (including ammonia), increase resistance to attack by oils, and provide reactive centers for cross-linking by divalent metal ions, diamines, or epoxides. 

The highest mechanical strengths are usually obtained when the fibre is used in fine fabric form but for many purposes the fibres may be used in mat form, particularly glass fibre. The chemical properties of the laminates are largely determined by the nature of the polymer but capillary attraction along the fibre-resin interface can occur when some of these interfaces are exposed at a laminate surface. In such circumstances the resistance of both reinforcement and matrix must be considered when assessing the suitability of a laminate for use in chemical plant. Glass fibres are most commonly used for chemical plant, in conjunction with phenolic resins, and the latter with furane, epoxide and, sometimes, polyester resins. 

Allylic alcohols can be converted to epoxy-alcohols with tert-butylhydroperoxide on molecular sieves, or with peroxy acids. Epoxidation of allylic alcohols can also be done with high enantioselectivity. In the Sharpless asymmetric epoxidation,allylic alcohols are converted to optically active epoxides in better than 90% ee, by treatment with r-BuOOH, titanium tetraisopropoxide and optically active diethyl tartrate. The Ti(OCHMe2)4 and diethyl tartrate can be present in catalytic amounts (15-lOmol %) if molecular sieves are present. Polymer-supported catalysts have also been reported. Since both (-t-) and ( —) diethyl tartrate are readily available, and the reaction is stereospecific, either enantiomer of the product can be prepared. The method has been successful for a wide range of primary allylic alcohols, where the double bond is mono-, di-, tri-, and tetrasubstituted. This procedure, in which an optically active catalyst is used to induce asymmetry, has proved to be one of the most important methods of asymmetric synthesis, and has been used to prepare a large number of optically active natural products and other compounds. The mechanism of the Sharpless epoxidation is believed to involve attack on the substrate by a compound formed from the titanium alkoxide and the diethyl tartrate to produce a complex that also contains the substrate and the r-BuOOH. ... 

Ali, F., Chang, Y., Kang, S.C., Yoon, J.Y. 2009. Thermal, mechanical and rheological properties of poly (lactic add)/epoxidized soybean oil blends. Polymer Bulletin. 62 91-98. 

Xu, Y. and Qu, J. 2009. Mechanical and rheological properties of epoxidized soybean oil plasticized poly(lactic acid). Journal of Applied Polymer Science 112 3185 - 3191. 

Hargreaves has suggested that the insolubilization of some closely related polymers is due to photolytic homolysis of the endoperoxide 0-0 bond and subsequent generation of carbon-centered radicals from the O radicals (19). There are several facts that make this an extremely unlikely explanation for the data described here these include the quantitative insufficiency of the maximum amount of endoperoxide reaction obtainable with a few hundred mJ/cm2 dose (homolysis quantum yield <0.5 (46), and extinction coefficient 1 (M cm)-1 (47)), and the synthetic utility of such homolysis reactions in related molecules in the presence of good hydrogen atom donors (implying facile epoxide formation) (48). Clearly the crosslinking observed under N2 is not accounted for by this mechanism. 

During the last three decades, peroxo compounds of early transition metals (TMs) in their highest oxidation state, like TiIV, Vv, MoVI, WV1, and Revn, attracted much interest due to their activity in oxygen transfer processes which are important for many chemical and biological applications. Olefin epoxidation is of particular significance since epoxides are key starting compounds for a large variety of chemicals and polymers [1]. Yet, details of the mechanism of olefin epoxidation by TM peroxides are still under discussion. 

Epoxides can react with alcohols via acidic or basic catalysed reaction mechanisms. However, since both strong acids and bases will degrade the cell wall polymers of wood, the reaction is usually catalysed via the use of amines, which are more strongly nucleophilic than the OH group. For example, whereas the production of epoxy-phenolic resins requires temperatures in the region of 180-205 °C, reaction between epoxides and primary or secondary amines takes place at 15 °C (Turner, 1967). Reaction of epoxides with wood often involves the use of tertiary amines as catalysts (Sherman etal., 1980). The sapwood is more reactive towards epoxides than heartwood (Ahmad and Harun, 1992). 

Some Mechanism Aspects of Epoxide Polymerisation. Stereochemical Structure of the Crystalline Polymers from the 2,3-Epoxybutanes. J. Polymer Sci. B 2, 1085 (1964). 

The problems associated with the multifunctional curing agents for CTPB and the resultant aging behavior of the cured polymers have led to a practical solution for curing binders and propellants—i.e., using mixed aziridines or a mixture of an aziridine and an epoxide. Such mixtures, when appropriately balanced, usually provide satisfactory mechanical behavior and high temperature stability. In dual curing systems such as MAPO and BITA or MAPO and a suitable multifunctional epoxide,... 

---