Phthalic anhydride, cross-linked with

Maleic and phthalic anhydrides with propylene glycol Cross-linked with free radical initiator and styrene... 

The free 2 OH s are then cross-linked with more molecules of phthalic anhydride. 

The curing (cross-linking) of the prepolymer can be achieved by either reaction with primary amines (often aromatic) which attack the epoxy end groups, or carboxylic acid anhydrides (e.g. phthalic anhydride) which react with the pendant hydroxy-groups. 

Smith condensed phthalic anhydride with glycerol in 1901 to prepare a glassy brittle material. Kienle in 1924 started investigating these resins and called them alkyds, He modified the polyesters with drying oils. By this modification they become soluble, on exposure to oxygen rapid cross-linking occurs and... 

An unsaturated polyester resin consists of a linear polyester whose chain contains double bonds and an unsaturated monomer such as styrene that copolymerizes with the polyester to provide a cross-linked product. The most common unsaturated polyester is made by step growth polymerization of propylene glycol with phthalic and maleic anhydrides. Subsequent treatment with styrene and a peroxide catalyst leads to a solid, infusible thermoset. 

This is a very broad class of compounds commonly used in coatings. Over 400-500 different alkyd resins are commercially available. They are polyesters containing unsaturation that can be cross-linked in the presence of an initiator known traditionally as a drier. A common example is the alkyd formed from phthalic anhydride and a glyceride of linolenic acid obtained from various plants. Cross-linking of the multiple bonds in the long unsaturated chain R produces the thermoset polymer by linking R groups of separate molecules with each other. 

Alkyds were synthesized by Kienle in the 1920s from trifunctional alcohols and dicar-boxylic acids. Unsaturated oils, called drying oils, were transesterified with the phthalic anhydride in the reaction so that an unsaturated polymer was obtained which could later be reacted producing a cross-linked product. 

Unsaturated polyesters have been produced from reaction of ethylene glycol with phthalic anhydride, or maleic anhydride (structure 4.46). These polyesters may be dissolved in organic solvents and used as cross-linking resins for the production of fibrous glass-reinforced composites ... 

The use of triols or tricarboxylic acids leads to cross-linked or network polyesters. For example, an alkyd resin is formed by the reaction of glycerol with phthalic anhydride [19]. 

These are comparatively soft materials and they are soluble in a number of organic solvents. Under more drastic conditions (200-220°) and with a larger proportion of phthalic anhydride, the Secondary alcohol groups are esterified and the simple chains become cross-linked three dimensional molecules of much higher molecular weight are formed ... 

The temperature of esterification has a significant influence on isomerization rate, which does not proceed above 50% at reaction temperatures below 150°C. In resins produced rapidly by using propylene oxide and mixed phthalic and maleic anhydrides at 150°C, the polyester polymers, which can be formed almost exclusively in the maleate conformation, show low cross-linking reaction rates with styrene. 

Thermosetting space-network polymers can be prepared through the reaction of polybasic acid anhydrides with polyhydric alcohols. A linear polymer is obtained with a bifunctional anhydride and a bifunctional alcohol, but if either reactant has three or more reactive sites, then formation of a three-dimensional polymer is possible. For example, 2 moles of 1,2,3-propane-triol (glycerol) can react with 3 moles of 1,2-benzenedicarboxylic anhydride (phthalic anhydride) to give a highly cross-linked resin, which usually is called a glyptal ... 

The resulting bisepoxy compounds are cross-linked cold with polyamines, if necessary with added accelerators. A hot cure can either be accomplished with amines or anhydrides (eg, phthalic acid anhydride). If suitable initiators are present, EP systems can also be cross-linked by radiation. 

Cross-linking Reaction of an Epoxy Resin with Phthalic Anhydride... 

Thermoset plastics have also been pyrolysed with a view to obtain chemicals for recycling into the petrochemical industry. Pyrolysis of a polyester/styrene copolymer resin composite produced a wax which consisted of 96 wt% of phthalic anhydride and an oil composed of 26 wt% styrene. The phthalic anhydride is used as a modifying agent in polyester resin manufacture and can also be used as a cross-linking agent for epoxy resins. Phthalic anhydride is a characteristic early degradation product of unsaturated thermoset polyesters derived from orf/io-phthalic acid [56, 57]. Kaminsky et al. [9] investigated the pyrolysis of polyester at 768°C in a fiuidized-bed reactor and reported 18.1 wt% conversion to benzene. 

There are two options for the other component of an epoxy resin system. Use of mono- or di-anhydrides as curing agents, usually catalyzed by a tertiary amine, causes reactions with the residual secondary hydroxyls in the repeating unit of the prepolymer forming esters and free carboxylic acids. The carboxylic acids formed also react with the epoxide end groups forming cross-links and further free secondary hydroxyl groups. Maleic anhydride, phthalic anhydride, or pyromellitic dianhydride are suitable for this process (Eq. 21.27). 

Solution As we shall see in Chapter 8, the copolymerization of maleic anhydride and styrene shows a strong tendency toward alternation (ri rj = 0.06). Consequently, a maleic anhydride-based unsaturated polyester cross-hnked with styrene forms a large number of short cross-links, resulting in a rigid polymer. With the addition of phthalic anhydride, the tendency toward alternation is reduced due to the occasional intervention of phthahc anhydride. The reduction of cross-link density results in a less rigid polymer. 

The saturated acid (phthalic anhydride) helps to reduce the cross-link density and, hence, the brittleness of the cured polyester resin. Resin composition can be varied so that product properties can be tailored to meet specific end-use requirements. For example, a resin with enhanced reactivity and improved stiffness at high temperatures is obtained by increasing the proportion of unsaturated acid. On the other hand, a less reactive resin with reduced stiffness is obtained with a higher proportion of the saturated acid. 

Cross-linked epoxy resins are combustible and their burning is self-supporting. They require mainly reactive flame-retardants, such as tetrachloro- or tetrabromobisphenol-A and various halogenated epoxides. Even the cross-linking agent may be flame-retardant, as in the case of chlorendic anhydride, tetrabromo- or tetrachloro-phthalic anhydride, or possibly phosphorus compounds. Halogenated agents can be supplemented with antimony trioxide. 

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