Ethylene glycol addition reaction

The copper-catalyzed reactions of aryl bromides were more effectively conducted with the hindered phenols 2,6-dimethylphenol (64) and 2-phenylphenol (65) as additive than with ethylene glycol. These reactions were conducted at 100 °C instead of 80 °C, as for the reactions of aryl iodides. Moreover, amine in large excess as solvent was required (equation 63). 

Considering the activity data of the different ATRP initiators presented in Fig. 3.4, using -hydroxylethyl a-bromoisobutyrate (HEBIB) as bifunctional initiator seemed reasonable and was synthesized according to White et al. [45]. Briefly, anhydrous ethylene glycol (90 ml, 1.6 mol) was cooled to 0 °C in a flame-dried two-neck round bottom flask. a-Bromoisobutyryl bromide (8 ml, 0.06 mol) was slowly added with an addition funnel to the stirring ethylene glycol. The reaction solution was stirred at 0 °C for three hours. Thereafter, the reaction was quenched with 40 ml of deionized water and extracted with chloroform (3 x 40 ml). The chloroform/product mixture... 

Condensation polymerization differs from addition polymerization in that the polymer is formed by reaction of monomers, each step in the process resulting in the elimination of some easily removed molecule (often water). E.g. the polyester polyethylene terephthalate (Terylene) is formed by the condensation polymerization (polycondensation) of ethylene glycol with terephthalic acid ... 

Acryhc stmctural adhesives have been modified by elastomers in order to obtain a phase-separated, toughened system. A significant contribution in this technology has been made in which acryhc adhesives were modified by the addition of chlorosulfonated polyethylene to obtain a phase-separated stmctural adhesive (11). Such adhesives also contain methyl methacrylate, glacial methacrylic acid, and cross-linkers such as ethylene glycol dimethacrylate [97-90-5]. The polymerization initiation system, which includes cumene hydroperoxide, N,1S7-dimethyl- -toluidine, and saccharin, can be apphed to the adherend surface as a primer, or it can be formulated as the second part of a two-part adhesive. Modification of cyanoacrylates using elastomers has also been attempted copolymers of acrylonitrile, butadiene, and styrene ethylene copolymers with methylacrylate or copolymers of methacrylates with butadiene and styrene have been used. However, because of the extreme reactivity of the monomer, modification of cyanoacrylate adhesives is very difficult and material purity is essential in order to be able to modify the cyanoacrylate without causing premature reaction. 

Dicylopentadiene Resins. Dicyclopentadiene (DCPD) can be used as a reactive component in polyester resins in two distinct reactions with maleic anhydride (7). The addition reaction of maleic anhydride in the presence of an equivalent of water produces a dicyclopentadiene acid maleate that can condense with ethylene or diethylene glycol to form low molecular weight, highly reactive resins. These resins, introduced commercially in 1980, have largely displaced OfXv o-phthahc resins in marine apphcations because of beneficial shrinkage properties that reduce surface profile. The inherent low viscosity of these polymers also allows for the use of high levels of fillers, such as alumina tfihydrate, to extend the resin-enhancing, fiame-retardant properties for apphcation in bathtub products (Table 4). 

When low boiling ingredients such as ethylene glycol are used, a special provision in the form of a partial condenser is needed to return them to the reactor. Otherwise, not only is the balance of the reactants upset and the raw material cost of the resin increased, but also they become part of the pollutant in the waste water and incur additional water treatment costs. Usually, a vertical reflux condenser or a packed column is used as the partial condenser, which is installed between the reactor and the overhead total condenser, as shown in Figure 3. The temperature in the partial condenser is monitored and maintained to effect a fractionation between water, which is to pass through, and the glycol or other materials, which are to be condensed and returned to the reactor. If the fractionation is poor, and water vapor is also condensed and returned, the reaction is retarded and there is a loss of productivity. As the reaction proceeds toward completion, water evolution slows down, and most of the glycol has combined into the resin stmcture. The temperature in the partial condenser may then be raised to faciUtate the removal of water vapor. 

The addition product, C QHgNa, called naphthalenesodium or sodium naphthalene complex, may be regarded as a resonance hybrid. The ether is more than just a solvent that promotes the reaction. StabiUty of the complex depends on the presence of the ether, and sodium can be Hberated by evaporating the ether or by dilution using an indifferent solvent, such as ethyl ether. A number of ether-type solvents are effective in complex preparation, such as methyl ethyl ether, ethylene glycol dimethyl ether, dioxane, and THF. Trimethyl amine also promotes complex formation. This reaction proceeds with all alkah metals. Other aromatic compounds, eg, diphenyl, anthracene, and phenanthrene, also form sodium complexes (16,20). 

The stmcture of individual block polymers is deterrnined by the nature of the initiator (1,2-propanediol above), the sequence of addition of propylene and ethylene oxides, and the percentage of propylene and ethylene oxides in the surfactant. Thus, when the order of addition is reversed, a different stmcture is obtained in which the hydrophobic moieties are on the outside of the molecule. With ethylene glycol as the initiator, the reactions are as foUows ... 

Ethylene bromohydrin has been prepared by the reaction between ethylene glycol and hydrobromic acid and phosphorus tribromide. It has also been prepared by the direct addition of hypobromous acid to ethylene, and by the reaction between ethylene and dilute bromine water. With ethylene oxide now available at a reasonable price, the method described is probably the best because of the high yields and the convenience of reaction. 

Alkyl fluorides have been prepared by reaction between elementary fluorine and the paraffins, by the addition of hydrogen fluoride to olefins, by the reaction of alkyl halides with mercurous fluoride, with mercuric fluoride, with silver fluoride, or with potassium fluoride under pressure. The procedure used is based on that of Hoffmann involving interaction at atmospheric pressure of anhydrous potassium fluoride with an alkyl halide in the presence of ethylene glycol as a solvent for the inorganic fluoride a small amount of olefin accompanies the alkyl fluoride produced and is readily removed by treatment with bromine-potassium bromide solution. Methods for the preparation of alkyl monofluorides have been reviewed. ... 

Tlie first suggestion of a template effect which was offered in the literature was made by Greene in 1972 °. Tlie illustration of this concept is approximately that shown in Eq. (2.2), above. Greene presented several pieces of evidence in addition to the concept itself. First, he noted that when the final concentration of 18-crown-6 in a reaction mixture (MejSO) was increased from 0.04 At to 0.09 Af, the yield of crown dropped only slightly (84% to 75%). In a competition experiment, equal amounts of 18-crown-6 and 21-crown-7 were formed when one molar equivalent each of triethylene glycol and tetra-ethylene glycol were allowed to compete for triethylene glycol ditosylate (KO-t-Bu/THF). 

Concerning the reaction of ACPC with diols, the frequent use of poly(ethylene glycol) has to be mentioned [20-24]. Ueda et al. ([22-24]) reacted preformed poly(ethylene glycol) (Mn between 6 x 10 to 2 x 10 ) with ACPC. In this case, unlike the reaction of ACPA with diols vide ante), no additional condensation agent was needed. The ethylene glycol-based thermally labile polymers were used to produce blocks with poly(vinyl chloride) [22], poly(styrene) [23], poly(methyl acrylate), poly(vinyl acetate), and poly(acrylonitrile) [24]. 

Polyaddition reactions based on isocyanate-terminated poly(ethylene glycol)s and subsequent block copolymerization with styrene monomer were utilized for the impregnation of wood [54]. Hazer [55] prepared block copolymers containing poly(ethylene adipate) and po-ly(peroxy carbamate) by an addition of the respective isocyanate-terminated prepolymers to polyazoesters. By both bulk and solution polymerization and subsequent thermal polymerization in the presence of a vinyl monomer, multiblock copolymers could be formed. 

Using excess ethylene glycol is the usual practice because it drives the equilihrium to near completion and terminates the acid end groups. This results in a polymer with terminal -OH. When the free acid is used (esterification), the reaction is self catalyzed. However, an acid catalyst is used to compensate for the decrease in terephthalic acid as the esterification nears completion. In addition to the catalyst and terminator, other additives are used such as color improvers and dulling agents. For example, PET is delustred hy the addition of titanium dioxide. 

Due to its commercial importance, the synthesis of copper phthalocyanine (PcCu) is the best investigated of all the phthalocyanines. Copper phthalocyanine is prepared from phthalonitrile and copper(I) chloride without solvent137 and also in a melt of urea.229,277 Additionally, the insertion of copper into metal-free phthalocyanine in butan-l-ol and pentan-l-ol is possible. The copper salts used in this case are copper(I) chloride112 and copper(II) acetate.290 Starting from copper(II) acetate, copper phthalocyanine can also be prepared in ethylene glycol.127 As mentioned above, copper phthalocyanine often occurs as a byproduct of the Rosenmund-von Braun reaction. To increase the yield of the phthalocyanine the solvent dimethylformamide can be substituted by quinoline. Due to the higher boiling point of quinoline, the copper phthalocyanine is the main product of the reaction of copper(I) cyanide and 1,2-dibromoben-zene.130... 

The principal solvolysis reactions for PET are methanolysis with dimethyl terephthalate and ethylene glycol as products, glycolysis with a mixture of polyols and BHET as products, and hydrolysis to form terephthalic acid and ethylene glycol. The preferred route is methanolysis because the DMT is easily purified by distillation for subsequent repolymerization. However, because PET bottles are copolyesters, the products of the methanolysis of postconsumer PET are often a mixture of glycols, alcohols, and phthalate derivatives. The separation and purification of the various products make methanolysis a cosdy process. In addition to the major product DMT, methanol, ethylene glycol, diethylene glycol, and 1,4-cyclohexane dimethanol have to be recovered to make the process economical.1... 

A method of converting polycarbonate (PC) to bishydroxyethyl ether of bisphenol A (BHE-BPA) was studied, with a view to recycling PC plastic wastes. Treating PC in ethylene glycol with a catalytic amount of sodium hydroxide produced the monohydroxyethyl ether of bisphenol A (MHE-BPA, 42%), BHE-BPA (11%) and BPA (42%). BHE-BPA was produced quantitatively when 1.6 mol. equiv. ethylene carbonate was added to this reaction system. The reaction of BPA with EC produced both BHE-BPA and MHE-BPA, indicating that ethylene carbonate was formed as an intermediate in the base catalysed reaction of PC with ethylene glycol. A large proportion of this ethylene carbonate formed from PC was, however, lost by decarboxylation so additional ethylene carbonate must be provided for the quantitative preparation of BHE-BPA. 12 refs. 

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