Epoxy resins Glycidyl ethers

In addition to the DGEB A resins, there are several other types of epoxy resins of commercial significance. The most common of these are epoxy novolacs, glycidyl ether of tetraphe-nolethane, bisphenol F-based resins, and aliphatic and cycloaliphatic resins. 

Glycidyl Ether of Tetraphenolethane. A large number of polyhydric phenols have been used to prepare diglycidyl ethers. The polyphenol, l l,2 2-(p-hydroxyphenol)ethane, is used to prepare a tetrafunctional epoxy resin, tetraglycidyl ether of tetraphenolethane. The functionality of commercial resins (e.g., EPON Resin 1031, Resolution Performance Products, LLC) is about 3.5. This forms a solid resin (melting point of 80°C) with a structure as shown in Fig. 2.6. Commercial products are solid resins and solutions. 

The viscosity of the epoxide prepolymers in many instances is reduced by additions of thin liquid epoxy compounds fliat may include cycloaliphatic epoxides or lactones. Various epoxidized vegetable oils, like epoxidized linseed, sunflower, soybean, and others are also used in some formulations. Table 3.4. lists come cycloaliphatic epoxy monomers used for such purposes. Vinyl ethers polymerize at a faster rate than do cycloaliphatic epoxides. They are, therefore, included in some formulations. Other materials fliat are included for such purposes or to control viscosity can be epoxy novolacs, glycidyl ethers of long chain alcohols. To control viscosity, polyols might also be used, because it is assumed that hydroxy group bearing compounds crosslink with the epoxy resins. 

There are two main categories of epoxy resins glycidyl epoxy, and non-glycidyl epoxy. The former are further classified as glycidyl-ether, glycidyl-ester and glycidyl-amine. 

TetrabromobisphenolA. TBBPA is the largest volume reactive flame retardant. Its primary use is in epoxy resins (see Epoxyresins) where it is reacted with the bis-glycidyl ether of bisphenol A to produce an epoxy resin having 20—25% bromine. This brominated resin is typically sold as a 80% solution in a solvent. TBBPA is also used in the production of epoxy oligomers which are used as additive flame retardants. 

Reactive (unsaturated) epoxy resins (qv) are reaction products of multiple glycidyl ethers of phenoHc base polymer substrates with methacrylic, acryhc, or fumaric acids. Reactive (unsaturated) polyester resins are reaction products of glycols and diacids (aromatic, aUphatic, unsaturated) esterified with acryhc or methacrylic acids (see POLYESTERS,unsaturated). Reactive polyether resins are typically poly(ethylene glycol (600) dimethacrylate) or poly(ethylene glycol (400) diacrylate) (see PoLYETPiERs). 

Polynuclear Phenol—Glycidyl Ether-Derived Resins. This is one of the first commercially available polyfunctional products. Its polyfunctionahty permits upgrading of thermal stabiUty, chemical resistance, and electrical and mechanical properties of bisphenol A—epoxy systems. It is used in mol ding compounds and adhesives. 

The cycloahphatic products are generally Hquids of lower viscosity than the standard glycidyl ether resins. The peroxidized resins contain no chlorine and low ash content and their ring-contained oxirane group (cyclohexene oxide type) reacts more readily with acidic curing agents than the bisphenol A-derived epoxy resins. 

Aliphatic Glycidyl Ethers. Aliphatic epoxy resins have been synthesized by glycidylation of difunctional or polyfunctional polyols such as a 1,4-butanediol, 2,2-dimethyl-l,3-propanediol (neopentyl glycol), polypropylene glycols, glycerol, trimethylolpropane, and pentaerythritol. 

Monofunctional aliphatic glycidyl ethers, eg, based on / -butanol or mixed Cg—alcohols, are used exclusively as reactive diluents to reduce viscosities of epoxy resin systems. Some loss of desirable cured properties results from the lowered functionality of the systems. 

Several other epoxy resins have been made. Many contain glycidyl ether group while others are cyclic aliphatic epoxies and acrylic aliphatic epoxies. 

Three workers applying an epoxy-based waterproofing paint containing glycidyl ether inside an underground water tank died in the tank of asphyxia. Constituents of epoxy resin will displace oxygen in a confined space and may have an independent narcotic effect on exposed workers. Strict precautionary measures are recommended under these conditions. ... 

We have also made an attempt to prepare lignin-epoxy resin adhesives (21). However, in order to improve its reactivity, kraft lignin was first phenolated with bisphenol-A. For phenolation, a small amount of aqueous hydrochloric acid or BF3-ethyl etherate was used as catalyst, and thus two kinds of glycidylation methods were adopted (21). The phenolation with bisphenol-A was found to enhance the solubility of the lignin derivative. In fact, the lignin-epoxy resins obtained were found to be completely soluble in certain organic solvents, including acetone. 

The epoxidalion is generally conducted in iwo steps (11 the polyol is added to cpichlorohydrin in the presence of a Lewis acid catalyst (stannic chloride, boron irifluoride) to pruduce the chlorollydrin intermediate, and (2] the intermediate is dchydrohalogenaled with sodium hydroxide iu yield the aliphatic glycidyl ether. Solid epoxy resins are prepared by the Taffy or Advancement processes. 

A rare example of cationic polymerization of emulsified epoxy resins has been reported by Walker et al.973 Polymerization of water emulsion of epoxy resins with a variety of superacids (triflic acid, HCIO4, HBF4, HPF6) results in polyols with two glycidyl units (294) in contrast to commercial epoxy resins with one unit separating the aromatic moieties. The level of residual glycidyl ether and Bisphenol-A units is also much lower than in conventional epoxy resins. 

Cold curing unsaturated resin was obtained in the following way. A mixture of BPA, BPA monocyanate and BPA dicyanate was cyclotrimerized and reacted with BMI. The obtained prepolymer with phenolic hydroxyls (cf. Scheme 9) was then treated with epichlorohydrin and alkali. The phenolic hydroxyls were thus transformed into glycidyl ether groups. Then the addition of methacrylic acid to the epoxy groups was carried out. The obtained vinyl ester (epoxyacrylate) type resin was dissolved in styrene and cured with the usual benzoyl peroxide/dimethylaniline system [131],... 

FIGURE 2.6 Chemical structure of glycidyl ether of tetraphenolethane epoxy resin. 

Glycidyl Ethers of Aliphatic Polyols. Glycidyl ether epoxy resins based on polyols provide greater flexibility and lower softening temperatures for the final cured epoxy system. The polyol is reacted with epichlorohydrin to produce these resins. These resins are generally not used alone because of water sensitivity and overall lack of toughness. However, they serve as modifiers for DGEBA-based epoxy resins. An idealized structure for a flexible resin based on this chemistry is shown in Fig. 2.9. 

Special grades of glycidyl ether epoxies have been made with components such as glycerol, polyglycols, pentaerythritol, and cashew nut oil. Other epoxy-polyglycidol resins have been produced from the reaction of epichlorohydrin and polyester polyol based on... 

Glycidyl ethers of aliphatic polyols based on polyglycol, glycerin, and other polyols are flexible epoxy resins. They are used as reactive diluents and flexibihzers for solvent-free epoxy resin formulations. Epoxy-polyglycol resins that are produced from the reaction of epichlorohydrin and polyester polyols based on ethylene or propylene oxide are the most common of these types of flexible epoxy resins. Examples of typical commercial aliphatic epoxy resins are shown in App. C. 

In adhesive formulations, aliphatic amines are most commonly used to cure the DGEBA type of epoxy resin. Aliphatic amines are not widely used with the non-glycidyl ether resins, since the amine-epoxy reaction is slow at low temperatures. The reaction usually requires heat and accelerators for an acceptable rate of cure. Aliphatic amines are primarily used with lower-viscosity DGEBA resins because of the difficulty in mixing such low-viscosity curing agents with the more viscous epoxy resins. 

Monofunctional epoxy diluents are used primarily with DGEBA epoxy blends. The most common monofunctional diluents are butyl glycidyl ether and phenyl glycidyl ether. The effect of butyl glycidyl ether and other reactive diluents on the viscosity of epoxy resin is shown in Fig. 6.3. Because the monofunctional diluents reduce crosslink density, they are used at relatively low levels to avoid degrading heat and chemical resistance or other properties of the adhesive. 

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