Epoxies development

Epoxies develop heat during their cure, resulting in a substantial increase in temperature in the reactive mixture. This temperature increase is known as an exotherm and is measured by a thermocouple. 

As has been mentioned in Chapter 2 the rate of curing of epoxy systems is temperature dependent and thus it is important to select a formulation appropriate to the ambient temperature during application. At 20 °C most epoxies develop 80% of their ultimate properties within 24 8 hours. 

Polymerization processes discovered in the 1920s resulted in a large number of new thermoplastics and elastomers, of which, in particular, polychloroprene, and polyisobutylene were used as the basis for new adhesive technologies. Polyurethanes and epoxies - developed in the mid-1930s - further broadened the range of adhesive raw materials. 

The first practical method for asymmetric epoxidation of primary and secondary allylic alcohols was developed by K.B. Sharpless in 1980 (T. Katsuki, 1980 K.B. Sharpless, 1983 A, B, 1986 see also D. Hoppe, 1982). Tartaric esters, e.g., DET and DIPT" ( = diethyl and diisopropyl ( + )- or (— )-tartrates), are applied as chiral auxiliaries, titanium tetrakis(2-pro-panolate) as a catalyst and tert-butyl hydroperoxide (= TBHP, Bu OOH) as the oxidant. If the reaction mixture is kept absolutely dry, catalytic amounts of the dialkyl tartrate-titanium(IV) complex are suflicient, which largely facilitates work-up procedures (Y. Gao, 1987). Depending on the tartrate enantiomer used, either one of the 2,3-epoxy alcohols may be obtained with high enantioselectivity. The titanium probably binds to the diol grouping of one tartrate molecule and to the hydroxy groups of the bulky hydroperoxide and of the allylic alcohol... 

Fig. 24. Representative cross-linking systems employed in negative tone CA resists, (a) Epoxy polymers requiring organic solvent development, (b) PHOST-based cross-linking systems requiring aqueous development, (c) Monomeric cross-linking agents used in PHOST matrix polymers.

Synthesis and Properties. Several polymers containing HFIP-O groups have been investigated, the most common beeing epoxies and polyurethanes. The development of fluorinated epoxy resins and the basic understanding of their chemistry has been reviewed (127). 

In addition to carbon and glass fibers ia composites, aramid and polyimide fibers are also used ia conjunction with epoxy resias. Safety requirements by the U.S. Federal Aeronautics Administration (FAA) have led to the development of flame- and heat-resistant seals and stmctural components ia civiUan aircraft cabias. Wool blend fabrics containing aramids, poly(phenylene sulfide), EDF, and other inherently flame-resistant fibers and fabrics containing only these highly heat- and flame-resistant fibers are the types most frequently used ia these appHcations. 

Studies of the particle—epoxy interface and particle composition have been helphil in understanding the mbber-particle formation in epoxy resins (306). Based on extensive dynamic mechanical studies of epoxy resin cure, a mechanism was proposed for the development of a heterophase morphology in mbber-modifted epoxy resins (307). Other functionalized mbbers, such as amine-terminated butadiene—acrylonitrile copolymers (308) and -butyl acrylate—acryhc acid copolymers (309), have been used for toughening epoxy resins. 

Alkylated phenol derivatives are used as raw materials for the production of resins, novolaks (alcohol-soluble resins of the phenol—formaldehyde type), herbicides, insecticides, antioxidants, and other chemicals. The synthesis of 2,6-xylenol [576-26-1] h.a.s become commercially important since PPO resin, poly(2,6-dimethyl phenylene oxide), an engineering thermoplastic, was developed (114,115). The demand for (9-cresol and 2,6-xylenol (2,6-dimethylphenol) increased further in the 1980s along with the growing use of epoxy cresol novolak (ECN) in the electronics industries and poly(phenylene ether) resin in the automobile industries. The ECN is derived from o-cresol, and poly(phenylene ether) resin is derived from 2,6-xylenol. 

Phenylenediamines are used in a variety of other appHcations, such as corrosion inhibitors, cross-linking agents for epoxy resins, toners for electrostatic image development (35), and to improve wrinkle resistance of cellulose acetate fibers (36). 

A variety of thermosetting resins are used in SMC. Polyesters represent the most volume and are available in systems that provide low shrinkage and low surface profile by means of special additives. Class A automotive surface requirements have resulted in the development of sophisticated systems that commercially produce auto body panels that can be taken direcdy from the mold and processed through standard automotive painting systems, without additional surface finishing. Vinyl ester and epoxy resins (qv) are also used in SMC for more stmcturaHy demanding appHcations. 

Disk thermistors can be produced to close limits of iaterchangeabihty, eg, 0.1 and 0.05° C. Disks cannot be made as small as the smallest beads 2 mm diameter seems an approximate practicable limit. Disks historically have been considered to be less stable than good beads. They are commonly protected with a coatkig of epoxy reski, which provides less compressive support than the glass coatkig of bead thermistors. More recent developments have resulted ki kiterchangeable glass-encapsulated disk thermistors which have the stabihty characteristics of the best beads. 

The energy required to initiate an explosion and the maximum explosive pressure developed by a number of polyester—epoxy powder coatings has been studied in some detail (89). The variables studied included composition, level and type of pigmentation, particle size, and concentration in air. The lowest MEG for unfilled and unpigmented powders was 33—35 g/m. ... 

Practical methods for synthesis and elucidation of the optimum physical forms were developed at Du Pont (13). The violets fill the void in the color gamut when the inorganics are inadequate. The quinacridones may be used in most resins except polymers such as nylon-6,6, polystyrene, and ABS. They are stable up to 275°C and show excellent weatherabiUty. One use is to shade phthalocyanines to match Indanthrone Blue. In carpeting, the quinacridones are recommended for polypropylene, acrylonitrile, polyester, and nylon-6 filaments. Predispersions in plastici2ers ate used in thermoset polyesters, urethanes, and epoxy resins (14). 

New efficient vulcanization systems have been introduced in the market based on quaternary ammonium salts initially developed in Italy (29—33) and later adopted in Japan (34) to vulcanize epoxy/carboxyl cure sites. They have been found effective in chlorine containing ACM dual cure site with carboxyl monomer (43). This accelerator system together with a retarder (or scorch inhibitor) based on stearic acid (43) and/or guanidine (29—33) can eliminate post-curing. More recently (47,48), in the United States a proprietary vulcanization package based on zinc diethyldithiocarbamate [14324-55-1]... 

To achieve low stress embedding material, low modulus material such as siUcones (elastomers or gels) and polyurethanes are usually used. Soft-domain elastomeric particles are usually incorporated into the hard (high modulus) materials such as epoxies and polyimides to reduce the stress of embedding materials. With the addition of the perfect particle size, distribution, and loading of soft domain particles, low stress epoxy mol ding compounds have been developed as excellent embedding materials for electronic appHcations. 

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