Poly allyl compounds

The polymers are used as molding resins for optical articles, since the transparency roughly corresponds to that of poly(methyl methacrylate), but the resistance to scratching and abrasion is about 3(T40 times better than in PMMA. Poly(diethylene glycol bisallyl carbonate) is used, for example, for the lenses of sunglasses. Since the cured resins have an electrical conductivity which is somewhere between those of porcelain and poly(tetra-fluoroethylene), they are used for electrical insulation. Prepolymer-soaked resin mats are obtainable commercially as Prepregs. 

Abraham, Asphalts and Allied Substances, 6th ed., Van Nostrand, Princeton, N.J., 1960. 

Hoiberg, Bituminous Materials Asphalts, Tar, and Pitches, Interscience, New York, 1964. P. L. Walker, Jr., ed.. Chemistry and Physics of Carbon, Marcel Dekker, New York, 1965, Vol. Iff. 

Donnet and A. Voet, Carbon Black—Physics, Chemistry, and Elastomer Reinforcement, Dekker, New York, 1976. 

Handbook of Polyolefin Fibers, Textile Book Service, London, 1967. 

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See Poly [oxy (methy l)sily lene] 1-Allyloxy-2,3-epoxypropane See other allyl compounds, i,2-epoxides... 

See Poly [oxy (methyl)sily lene] l-Allyloxy-2,3-epoxypropane See Other ALLYL COMPOUNDS, 1,2-EPOXIDES... 

Subsequent studies on BD polymerization by the solvent-free allyl compound Nd( ]3-C3H5)3 (without cocatalysts added) showed that—depending on monomer concentration—2 to 3 poly(butadiene) chains are generated per Nd-atom [291], By the addition of cocatalyst the number of chains generated per Nd-atom is reduced to one. 

A general synthesis for all diastereomeric L-hexoses, as an example for monosaccharides that often do not occur in the chiral pool, has been worked out. The epoxidation of allylic alcohols with tertiary butyl hydroperoxide in presence of titanyl tartaric ester catalysts converts the carbon-carbon double bond stereose-lectively to a diol and is thus ideally suited for the preparation of carbohydrates. The procedure is particularly useful as a repetitive two-carbon homologiza-tion in total syntheses of higher monosaccharides and other poly hydroxy compounds. It starts with a Wittig reaction of a benzylated a-hydroxy aldehyde with (triphenylphosphoran-ylidene)acetaldehyde to produce the olefinic double bond needed for epoxidation. Reduction with sodium-borohydride... 

S. David, A. Thieffiy, and A. foyli ses, A mild procedure for the regiospecific benzylation and allylation of poly-hydroxy-compounds via their stannylene derivatives in non-poiar solvents, J. Chan. Soc. Perkin Trans. 7 1796 (1981). 

The polymerization of allyl acetate has been studied reasonably extensively in the effort to elucidate the mechanisms of the polymerization process. The utility of poly(allyl acetate) as a resin is believed to be negligible. Nevertheless, this compound has been polymerized in bulk, in solution, and in emulsion. There is mention of a cationic polymerization process and of radiation-induced charge-transfer processes. 

As shown above many allylic compounds can be used for catalytic reactions with different reactivity. Allylic esters such as carbonates, acetates, and phosphates are widely used. Allylic acetates and phosphates react in the presence of bases such as EtsN and AcONa. However, Giambastiani and Poli reported that allylation of -keto esters, but not malonates, with allylic acetates can be carried out under neutral conditions, although the reaction is slower [5]. 

Compounds possessing allylic structures polymerize by free-radical mechanism only to low molecularweight oligomers. In some cases the products consist mostly of dimers and trimers. The DP for poly(allyl acetate), for instance, is only about 14. This is due to the fact that allylic monomer radicals are resonance-stabilized to such an extent that no extensive chain propagations occur. Instead, there is a large amount of chain transferring. Such chain transferring essentially terminates the reactions [151]. The resonance stabilization can be illustrated on an allyl alcohol radical ... 

The addition of allylstannanes to aldehydes with LPDE has been developed (Scheme 3.19) [44]. Chelation-controlled diastereoselective reactions are reported. Also wide functional group compatibility of LPDE is demonstrated in the allylation of poly oxygenated compounds including dialdose derivatives. 

As stated in section I, the termination mode of the particular monomer determines the number of functionalities per macromolecular chain. Most monomers undergo both unimolecular and bimolecular termination reactions. It is often observed that both respective monofunctional and bifunctional polymers are formed and well-defined functional polymers cannot be prepared. The use of allylmalonic acid diethylester in free-radical polymerization has been proposed to overcome the problems associated with the aforementioned functionality. In the presence of the allyl compound, the free-radical polymerization of monomers, regardless of their termination mode, proceeds entirely with the unimolecular termination mechanism, as shown in Scheme 9. Because allyl compounds lead to degradative chain transfer, the resulting allyl radical is quite stable due to the allyl resonance. Monofunctional polystyrene, polyvinylacetate, and poly(t-butyl methacrylate) were prepared by using this approach [33]. Subsequently, various macromonomers were derived from these polymers. 

Allyl polymers are made by free-radical polymerization of diaHyl compounds, most frequently diallyl dimethyl ammonium chloride (DADMAC) [7398-69-8] forming a chain containing a five-membered ring (28) poly(DADMAC) [26062-79-3]. 

Mention may also be made here of a number of polyfunctional compounds such as allyl methacrylate and glycol dimethacrylates which have been used to produce a cross-linked sheet of enhanced heat resistance compared with conventional poly(methyl methacrylate). Some manufacturers supply the sheet in an incompletely cross-linked state which allows a limited amount of forming after which the sheet may be further heated to complete the cure. 

Microwave-mediated transesterification of commercially available neat poly(styr-ene-co-allyl alcohol) with ethyl 3-oxobutanoate, ethyl 3-phenyl-3-oxopropanoate, and diethyl malonate provided the desired polymer-supported /i-dicarbonyl compounds (Scheme 12.18) [65]. Multigram quantities of these interesting building blocks for heterocycle synthesis were obtained simply by exposing the neat mixture of reagents to microwave irradiation in a domestic microwave oven for 10 min. 

Scheme 12.18 Derivatization of poly(styrene-co-allyl alcohol) with R = Me, Ph, OEt /7-dicarbonyl compounds.

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