Glycidyl ether

The 2-azo derivative (322), when heated with butyl glycidyl ether in acetic acid, reacts through the ring nitrogen (Scheme 186) (585). 

Poly(epichlorohydrin-co-ethylene oxide-co-allyl glycidyl ether) [26587-37-1... 

Polypropylene oxide-co-epichlorohydrin-co-allyl glycidyl ether)[25213-15-4... 

Resin and Polymer Solvent. Dimethylacetamide is an exceUent solvent for synthetic and natural resins. It readily dissolves vinyl polymers, acrylates, ceUulose derivatives, styrene polymers, and linear polyesters. Because of its high polarity, DMAC has been found particularly useful as a solvent for polyacrylonitrile, its copolymers, and interpolymers. Copolymers containing at least 85% acrylonitrile dissolve ia DMAC to form solutions suitable for the production of films and yams (9). DMAC is reportedly an exceUent solvent for the copolymers of acrylonitrile and vinyl formate (10), vinylpyridine (11), or aUyl glycidyl ether (12). 

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. 

The consumption of 4-/ f2 -butylphenol in the production of phenohc resins represents an appHcation in a mature market and Htfle growth is projected. Its use in end-capping polycarbonates, in the production of glycidyl ethers, and in the production of nucleation agents for polypropylene is expected to grow at a rate above the growth of the GNP (see Table 3). 

Ahyl alcohol undergoes reactions typical of saturated, aUphatic alcohols. Ahyl compounds derived from ahyl alcohol and used industriahy, are widely manufactured by these reactions. For example, reactions of ahyl alcohol with acid anhydrides, esters, and acid chlorides yield ahyl esters, such as diahyl phthalates and ahyl methacrylate reaction with chloroformate yields carbonates, such as diethylene glycol bis(ahyl carbonate) addition of ahyl alcohol to epoxy groups yields products used to produce ahyl glycidyl ether (33,34). 

Property AHyl chloride AHyl acetate AHyl methacrylate AHyl glycidyl ether AGE AHyl amine dimethyl ally amine dmaa "... 

AHyl glycidyl ether. Dimethyl ally] amine. 

Allyl Glycidyl Ether. This ether is used mainly as a raw material for silane coupling agents and epichlorohydrin mbber. Epichlorohydrin mbber is synthesized by polymerizing the epoxy group of epichlorohydrin, ethylene oxide, propylene oxide, and aHyl glycidyl ether, AGE, with an aluminum alkyl catalyst (36). This mbber has high cold-resistance. 

Although much research has been carried out with aHyl ethers there has been only limited commercial use (1). Multifimctional aHyl glycidyl ether [106-92-3],... 

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). 

In 1957, it was discovered that organometaUic catalysts gave high mol wt polymers from epoxides (3). The commercially important, largely amorphous polyether elastomers developed as a result of this early work are polyepichlorohydrin (ECH) (4,5), ECH—ethylene oxide (EO) copolymer (6), ECH—aUyl glycidyl ether (AGE) copolymer (7,8), ECH—EO—AGE terpolymer (8), ECH—propylene oxide (PO)—AGE terpolymer (8,9), and PO—AGE copolymer (10,11). The American Society for Testing and Materials (ASTM) has designated these polymers as follows ... 

AGE-Gontaining Elastomers. ECH—AGE, poly(epichlorohydrin-fo-allyl glycidyl ether) [24969-09-3] (3), ECH—EO—AGE, poly(epichlorohydrin- (9-ethylene oxide-i (9-allyl glycidyl ether) [26587-37-1] (4), ECH—PO—AGE, and PO—AGE are also amorphous polymers. 

Crystallinity is low the pendent allyl group contributes to the amorphous state of these polymers. Propylene oxide homopolymer itself has not been developed commercially because it cannot be cross-baked by current methods (18). The copolymerization of PO with unsaturated epoxide monomers gives vulcanizable products (19,20). In ECH—PO—AGE, poly(ptopylene oxide- o-epichlorohydrin- o-abyl glycidyl ether) [25213-15-4] (5), and PO—AGE, poly(propylene oxide-i o-abyl glycidyl ether) [25104-27-2] (6), the molar composition of PO ranges from approximately 65 to 90%. 

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. 

Triglycidyl derivative of aminophenol (7). Tetraglycidyl derivative of methylenedianiline (5) (6). Polynuclear phenol glycidyl ether (4) (4). 

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. 

The epoxidation is generally conducted in two steps (/) the polyol is added to epichlorohydrin in the presence of a Lewis acid catalyst (stannic chloride, boron triduoride) to produce the chlorohydrin intermediate, and (2) the intermediate is dehydrohalogenated with sodium hydroxide to yield the aliphatic glycidyl ether. A prominent side-reaction is the conversion of aliphatic hydroxyl groups (formed by the initial reaction) into chloromethyl groups by epichlorohydrin. The aliphatic glycidyl ether resins are used as flexibilizers for aromatic resins and as reactive diluents to reduce viscosities in resin systems. 

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. 

Because of processing problems 2-chloroethyl vinyl ether has now been replaced with other cure site monomers. These include vinyl and allyl chloracetates and allyl glycidyl ether. 

Vulcanisation can be effected by diamines, polyamines and lead compounds such as lead oxides and basic lead phosphite. The homopolymer vulcanisate is similar to butyl rubber in such characteristics as low air permeability, low resilience, excellent ozone resistance, good heat resistance and good weathering resistance. In addition the polyepichlorohydrins have good flame resistance. The copolymers have more resilience and lower brittle points but air impermeability and oil resistance are not so good. The inclusion of allyl glycidyl ether in the polymerisation recipe produces a sulphur-curable elastomer primarily of interest because of its better resistance to sour gas than conventional epichlorhydrin rubbers. 

These include copolymers of propylene sulphide with 3-10% of allyl glycidyl thioether and which may be considered as a thio-analogue of the propylene oxide-allyl glycidyl ether rubber briefly mentioned in Section 19.5 ... 

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