Allyl glycidyl ether reaction

Vinyl epoxides represent another class of compounds known to participate in CM reactions mediated by ruthenium NHG catalysts. The reactivity of these catalysts is unique, as catalyst 2 is typically limited to allyl glycidyl ether ... 

Fischer 39 40> did not observe any effect of allyl alcohol on the copolymerization of allyl glycidyl ether with phthalic anhydride. Reaction rates were identical and indpendent of proton donor concentration. This finding indicates that the presence of... 

In a first step the epoxy-functionalized siloxanes were prepared by hydrosilylation, with allyl glycidyl ether and Lamoreaux catalyst (Pt catalyst resulting from HjPtClg.H O in octanol), at 130-145°C for 4-lOh. The reaction is quantitative. 

Zak et al. [95] derived a mathematical description of the kinetics of polymerization of THF with 2% allyl glycidyl ether initiated by triiso-butylaluminium and water. The approach is quite different from that reported for these polymerizations by others. In their calculations they regard their system as a homopolymerization of THF and introduce the corresponding simplifying assumptions into their calculations of the kinetic parameters. They consider the usual propagation reaction and conclude that their polymerization can be adequately represented by the equation... 

High catalytic activity of dimeric complex 1 in the hydrosilylation of allyl esters and allyl ethers (as well allyl glycidyl ether) has been shown in Ref. [18]. The catalytic activity of rhodium-siloxide-phosphine complexes depends on the steric effects of the siloxy group and stereoelectronic effects of the trisubstituted phosphine [14]. Comparison of catalytic activity of dimeric (1) and monomeric, phosphine (2, 3) and non-phosphine (4) rhodium siloxide complexes in the examined reaction is presented in Table 1. 

All complexes have shown high catalytic activity, even at room temperature (in contrast to platinum catalysts). Hydrosilylation in the presence of phosphine-rhodium complexes occurred in air, because real catalyst (active intermediate) was formed after oxygenation and/or dissociation of phosphine, as reported previously [14]. The non-phosphine complexes 1 and 4 are also very efficient catalysts for the hydrosilylation of allyl glycidyl ether. Irrespective of the starting precursor, a tetracoordinated Rh-H species, responsible for catalysis, is generated under reaction conditions, as illustrated in Scheme 3. 

Hydrosilylation is also one of the basic methods for synthesis of modifying silicones. The rhodium siloxide complexes have been used in the reaction between heptamethyltrisiloxane and allyl glycidyl ether, which is a modeling reaction of the polymeric system (Eq. 2). 

A number of chlorinated poly(ethers) have practical uses. A common compound from this group is polyepichlorohydrin, [-CH(CH2CI)CH20-]n. Polyepichlorohydrin has practical applications as an elastomer and is used in copolymers with propylene oxide, ethylene oxide, allyl glycidyl ether (1-allyloxy-2,3-epoxypropane), etc. Another example is poly oxy[2,2 -bis(chloromethyl)-1,3-propandiyl] or poly[oxy-1,3-(2,2 -dichloromethyl)propylene], CAS 25323-58-4, which can be used as inert lining material for chemical plant equipment, as adhesive, coating material, etc. This macromolecule can be prepared starting with pentaerythritol in the sequence of reactions shown below ... 

In the patent specification [147] there data on the chemical attachment to hydridesilica surface in the presence of the Reney nickel, chloroplatinic acid or metallic platinum deposited on activated carbon as a catalyst of the following unsaturated functional compounds divinylbenzene, ethylene glycol diacrylate, acetylene, allyl alcohol, allyl glycidyl ether, allyl isocyanate, acrylic acid. The chemical reactions result in the transformation of Si-H bonds of hydridesilica surface into Si-C bonds. Such transformations may be also classified as processes of solid-phase catalytic hydrosilylation of functional olefins. 

Polymerizations. Isocyanurate polymer formation was catalyzed by the addition of N,N,N, N -tetramethyl-l,3-butanediamine and allyl glycidyl ether (redistilled) 1% (by weight) of each catalyst was used. Polymerization occurred at 25° to 50°C under anhydrous conditions although temperatures of 100° to 150° C were needed to complete the reaction with the short chain diisocyanate intermediates used. 

One of the older methods to obtain macromers is to add very small quantities of a monomer having a double bond and a polymerisable epoxy group in the same structure to propylene oxide, during the anionic polymerisation. A typical example of such a kind of monomer is allyl glycidyl ether. This monomer copolymerises anionically with PO, giving polyethers with small quantities of lateral double bonds (reaction 6.10). 

Another chemical system that has been investigated is the reaction of wood with maleic anhydride and allyl glycidyl ether (12),... 

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

In the modification reaction using the reaction of hydrosilylation, the authors successfully used trimethylsiloxy end blocked methylhydridesiloxanes [38, 39]. By hydride addition of unsaturated organic compounds, allyl glycidyl ether [40,41], allyl alcohol [42,43] or dicyclopentadiene [39,44] to methylhydridesiloxanes in the presence of a catalyst, comb-type methylsiloxane copolymers has been obtained. 

Rhodium-siloxide complex [ (diene)Rh(p-OSiMe3) 2] (I) appeared to be a very effective catalyst of the hydrosilylation of various allyl ethers for example, hydrosilylation of allyl glycidyl ether, allyl butyl ether, allyl phenyl ether and allyl benzyl ether [9] proceeds almost quantitatively even at room temperature (Table 1). The hydrosilylation of allyl glycidyl ether by triethoxysilane leads to glycidoxypropyltriethoxysilane, which is a commercially important silane coupling agent. The reaction of allyl ethers with hydrosiloxanes catalyzed by I also occurs with very high yield (Table 2) [10]. The hydrosilylation products have applications in the cosmetic industry [11]. 

Phosphonate monomers of type 1 were made from the reaction of allyl glycidyl ether with hydroxy-functionalized phosphonic acid. To obtain azo-phosphonated products (type 2), multicomponent reactions (amine-, aldehyde/ketone-, or phosphorus-containing compounds) such as the Kabachnick-Fields," Mannich," or Moedritzer ° reactions, were used. These reactions generated in a selective way the a-aminoallq lphosphonate products. 

Allyl glycidyl ether (VI) and glycidyl methacrylate (VII) were used to etherify wood blocks of Pinus sylves-tris and mechanically pulped spruce flbres. The mechanism of the reaction consisted in the chain extension of the wood OH functions by the epoxy groups of VI and VII. The modified samples were characterized by FTIR and C-NMR spectroscopy and by weight gain, which amounted to 7 and 20 per cent for VI and VII, respectively [12]. 

During the hydrosilylation of allyl glycidyl ether with l,4-bis(dimethylsilyl)benzene, or diphenylsilane in isothermal condition by calorimetric method at various concentration of initial compounds and catalyst the hydrosilylation rate constants and reaction order have been calculated [69]. 

SCHEME 12. HYDROSILYLATION REACTION OF METHYLHYDRIDESILOXANE TO ALLYL GLYCIDYL ETHER, IN THE PRESENCE OF CATAL YSTS. 

Table 1. Catalytic systems (Catalyst 1-9) used in copolymerization reactions of propylene oxide with allyl glycidyl ether...

The selectivity of these reactions is indicated by the disappearance at an equal rate of anhydride and epoxide from a model system based on allyl glycidyl ether [9]. 

In another approach, to minimize air inhibition, reactive oxygen species are added to the system, which preferentially consume oxygen before it can interfere with the curing reaction. Allyl ethers such as trimethylolpropane diallyl ether, pentaerythritol monoallyl ether and allyl glycidyl ether are normally used for this purpose. 

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