Diallyl maleate with

Paper coating latex binder based on the copolymerization of pre-emulsified vinyl acetate and diallyl maleate with ethylene under pressure [136]. 

Vinyl acetate - ethylene - NMAM - diallyl maleate copolymers, optional]y with itaconio acid, give films which cure rapidly at 132 (9) Other Copolymers with this acid are carpet backsizes.( )... 

Highly purified diallyl maleate and fumarate in an inert atmosphere, are said to polymerize very rapidly [118], However, trace impurities and atmospheric oxygen substantially reduce the polymerization rate under ordinary circumstances. Naturally with the double bond between the two carboxylate groups and the two allylic double bonds, crosslinking takes place at very low conversion. Even so, in copolymer systems such as in poly(vinyl acetate) emulsion copolymers, the cross-linking of a fumarate or maleate within the latex particles appears not to interfere significantly with film formation properties. As a matter of fact these monomers are incorporated in poly(vinyl acetate) latices used in adhesives and in water-based paints. 

Prepolymers of diallyl maleate have been prepared although not as readily as the prepolymers of the diallyl phthalates. A composition of 80% diallyl maleate prepolymer and 20% monomeric diallyl monomer with 3% dibenzoyl peroxide forms a hard transparent resin when subjected to 90°C at 2000 psi for 20 min [119]. 

Use of diallyl phthalate and diallyl maleate copolymers with vinyl chloride as rubbery sealants [135]. 

The first step involves the platinum catalyzed hydrosilylation of diallyl maleate (DAM) with trichlorosilane. By purifying the DAM and using Karstedfs Pt catalyst, one obtains the bis-trichlorosilyl intermediate in > 98% yield. The utilization of diallyl fumarate in this step does not provide significant advantage over the maleate isomer. 

Typically, these curable systems will employ reversible inhibitors, such as diallyl maleate (DAM), which coordinate with the platinum catalyst to prevent premature polymerization. At elevated temperatures, these platinum-inhibitor complexes dissociate and allow for the hydrosilylation reaction to occur. 

Of interest is the synthesis of the bis-(3-trimethoxysilylpropyl)fumarate, which is utilized as a low molecular weight polymer additive in a variety of silicone applications Prior to the present investigation, this compound was synthesized through a two-step process starting with commercially available diallyl maleate This reaction consistently generated a yellow/brown product with erratic yields of < 80% of the theoretical value. 

Selective free-radical polyaddition of dithiols to the allylic double bonds of diallyl maleate results in the synthesis of unique sulfur containing polyester with maleic unsaturation.In the presence of base, Michael-type addition of the thiol group with the maleate double bond occurs. The unsaturated polyester may be crosslinked both by vinyl monomers, such as styrene, with peroxides or with polythiols in the presence of base. 

Preferential and partial formation. A 23-28%-soln. of peracetic acid in ethyl acetate or acetone added with stirring during 1-3 hrs. at 40° to allyl 6-methyl-3-cyclohexenecarboxylate, when the reaction is found to be essentially complete by iodometric analysis after 2.5 hrs. the mixture added dropwise to a still kettle containing ethylbenzene under reflux at 30-50 mm pressure with distillation of solvent, excess peracetic acid, ethylbenze, and acetic acid the concentration of which is thus kept at a minimum allyl 3,4-epoxy-6-methylcyclohexanecarb-oxylate. Y 86%.—Similarly with a large excess of diolefin Diallyl maleate at 50° during 11.5 hrs. —allyl glycidyl maleate. Y 71%. F. e. s. F. G. Frostick, Jr., B. Phillips, and P. S. Starcher, Am. Soc. 81, 3350 (1959). 

Figure 6.5 Reaction of wood with maleic anhydride (MA) (a), and subsequent reaction of maleated wood with diallyl phthalate in the presence of benzoyl peroxide (BPO) (b).

Although they lack commercial importance, many other poly(vinyl acetal)s have been synthesized. These include acetals made from vinyl acetate copolymerized with ethylene (43—46), propylene (47), isobutylene (47), acrylonitrile (48), acrolein (49), acrylates (50,47), allyl ether (51), divinyl ether (52), maleates (53,54), vinyl chloride (55), diallyl phthalate (56), and starch (graft copolymer) (47). 

The diallyl esters of maleic and fumaric acid have found application primarily in copolymer systems. Considering that the distance between the two allyl groups of the maleate ester is similar to those of the o-phthalate, and that of the fumarate is geometrically quite different, it is unfortunate that there seems to have been no study of the cyclopolymerization possibilities of these monomers. In addition there are the problems associated with the copolymerization of an allyl grouping with the double bond of the maleic or fumaric moieties within the same molecule. 

Butenedioic acid, dibutyl ester. See Dibutyl maleate 2-Butenedioic acid, dimethyl ester. See Dimethyl maleate 2-Butenedioic acid, (Z)-, dioctyl ester. See Dioctyl maleate 2-Butenedioic acid (E)-, di-2-propenyl ester. See Diallyl fumarate 2-Butenedioic acid, polymer with methoxyethene, butyl ester. See PVM/... 

Free-radical cyclopolymerization of diallyl or mixed allyl-vinyl and allyl-acrylic derivatives has been investigated. Particularly, Jansen has studied the photo-initiated copolymerization of various commercial vinylethers as well as allylethers with fumarates or maleates. Real-time infrared spectroscopy with advanced multivariate statistical techniques was used for the determination of copolymerization reactivity ratios of... 

Hydrosilylation. Historically, the synthesis of the silyl chloride intermediate from DAM and TCS requires between 100-200 ppm of platinum. Often, the hydrosilylation would terminate prior to completion, with yields as low as 40%. To determine whether DAM was responsible for poor reaction results, the diallyl fumarate (DAF) isomer was evaluated as an alternate substrate DAF is a weaker inhibitor of platinum The comparison revealed that when the DAF and DAM were distilled prior to use, there were no significant differences in reaction kinetics. It was determined that a sulfur contaminant found in commercial sources of DAM - assumed to be a residual of acid catalyst from the maleate esterification - results in poisoning of the platinum catalyst. Thus with distillation, DAM can now be hydrosilylated with TCS in the presence of only 10 ppm platinum catalyst. This observation was consistently reproduced when utilizing an active platinum catalyst complex. Consequently, the hydrosilylation offers > 99% yield with respect to depletion of either DAF or DAM, and severe coloration is completely eliminated from the final product by reduction of the amount of platinum catalyst required. 

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