Allyl compound copolymerization

Bartlett, P. D., and K. Nozaki Polymerization of allyl compounds. III. The peroxide-induced copolymerization of allyl acetate with maleic anhydride. J. Amer. chem. Soc. 68, 1495 (1946). 

The free radical copolymerization of methyl methacrylate or acrylonitrile in the presence of zinc chloride with allylic compounds such as allyl alcohol, allyl acetate, and allyl chloride or butene isomers such as isobutylene, 1-butene, and 2-butene is characterized by the incorporation of greater amounts of comonomer than is noted in the absence of zinc chloride (35). Analogous to the radical homopolymerization of allylic monomers in the presence of zince chloride, the increase in the electron-accepting capability of the methyl methacrylate or acrylonitrile as a result of complexation results in the formation of a charge transfer complex which undergoes homopolymerization and/or copolymerization with a polar monomer-complexed polar monomer complex. 

TABLE XVIII Copolymerization of Allyl Compounds with Sulfur Dioxide... 

Apparently, the driving force for the ring opening is the relief of the strain in the spiro system and the formation of the stable carbonate double bond. The double ring opening is probably a concerted process from the initial radical addition product to the open-chain radical. Even though the spiro compound XI is an allyl monomer, it does copolymerize with a wide variety of comonomers. 

Carbohydrates remain an attractive source of chirality in preparation of ligands for asymmetric catalysis. Functionalized phospholanes, 192 [167], and chiral bisphosphinites 193 [168] with an attached crown ether unit were obtained recently from D-mannitol and from phenyl 2,3-di-0-allyl-4,6-0-benzylidene-p-D-glucopyranoside, respectively (Figure 18). Compounds 194 and 195 were obtained in the photochemical addition of H2P(CH2)3PPH2 onto the crresponding alkenes - Pd-complexes of these new bisphosphines were successfully applied as catalysts in the copolymerization of CO and... 

The best materials are produced by curing unsaturated polyester during copolymerization with different types of unsaturated monomers and oligomers, such as styrene and its derivatives, methyl methacrylate, vinylacetate, sulfone-type compounds, allyl esters, and oligo(ester acrylates).5... 

Dolgoplosk et al. [301] have reported kinetic data on the polymerization of dienes using 7r-allylic (7r-allyl and TT-crotyl) chromium compounds in solution and deposited on a silica support, and on the copolymerization of butadiene and isoprene using the supported TT-allyl catalyst and a Cr03/Si02 Al2 03 catalyst. Full details of the kinetics. 

Several ligands were used with allyl-type and vinyl-type initiators, such as 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMDETA), NJJyN JJ jN -pentamethyldiethylenetriamine (PMDETA), or compound 7 in Scheme 66. Zeng et al. showed that the combination of initiator 1 in Scheme 66 with BA6TREN or initiator 4 in Scheme 66 with BA6TREN gave the best control of the molar mass for the ATRP of 2-(dimethylamino)ethyl methacrylate. These allylic macromonomers are then able to copolymerize with acrylamide. 

A rise in the content of hydroxyl groups and double bonds was, however, observed during copolymerization without HA compounds by Tanaka and Kakiuchi . These groups and unsaturation can arise by base — or acid-catalyzed isomerization of epoxides to allyl alcohol derivatives (and references cited therein). In the... 

In an old patent, Friedman prepared homopolymers from cyclic phosphites and phosphonates with allyl functions (Scheme 3.12). These compounds were homopolymerized or copolymerized with other monomers such as styrene or acrylate monomers in the presence of conventional initiators or from UV activation. The polymers produced quite tough, hard, colorless and clear non-burning plastics. 

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