Diallyl fumarate

Among the preformed polymers cured by minor additions of aHyl ester monomers and catalysts followed by heat or irradiation are PVC cured by diallyl fumarate (82), PVC cured by diallyl sebacate (83), fluoropolymers cured by triaHyl trimeUitate (84), and ABS copolymers cured by triaUyl trimeUitate (85). 

Property AHyl methacrylate, AMA Diallyl male ate, DAM Diallyl fumarate, DAI... 

Using differential scanning calorimetry, studies on the isothermal bulk polymerization of diallyl fumarate, diallyl maleate, and diallyl succinate were carried out. 

At a concentration of 2,2 -azobisisobutyronitrile of 0.0225 mole/liter of diallyl fumarate, the heat of isothermal bulk polymerization at 75°C was found to be — 63.6kJ/mole (-15.2 kcal/mole). At 96°C it was — 87.9kJ/mole (-21.0 kcal/mole). Similar decreases in the heat of polymerization were also noted at high levels of initiator over the same temperature range. 

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/... 

Fumaric acid, diallyl ester. See Diallyl fumarate Fumaric acid, dibutyl ester. See Dibutyl fumarate Fumaric resin. See Maleic resin Fumed silica Fumed silicon dioxide. See Silica, fumed Fural 2-Furaldehyde Furale. See Furfural... 

Butenedioic acid (E)-, di-2-propenyl ester. See Diallyl fumarate... 

Diallyl dimethyl ammonium chloride. See Dimethyl diallyl ammonium chloride Diallyidimethyl ammonium chloride with acrylamide. See Polyquatemium-7 Diallyidimonium chloride/hydroxyethylcellulose copolymer. See Polyquatemium-4 Diallyl disulfide. See Allyl disulfide Diallyl ester acetic acid. See Diacetone acrylamide Diallyl fumarate CAS 2807-54-7... 

Cobalt acetylacetonate DEDM hydantoin Diallyl chlorendate Diallyl fumarate Dicyclopentenyl methacrylate Diethylaminoethyl acrylate Diethylene glycol divinyl ether Di-(2-methy I benzoyl) peroxide ... 

Diallyl fumarate SR 204 2809-21-4 Aquacid-105 EX Aquanate 110 Belclene 660 BoilerGUARD 3660 Briquest ADPA-60A Briquest ADPA-60AW Dequest 2010 Etidronic acid Feliox 115 Fostex P... 

C10H12O3 P-Anisyl acetate Benzaldehyde glyceryl acetal Ethyl o-anisate Ethyl-p-anisate Ethyl phenoxyacetate Isopropylparaben Propyl 2-furanacrylate Propylparaben C10H12O3 K Potassium propylparaben C10H12O4 Diallyl fumarate Diallyl maleate Ethyl vanillate Maltyl isobutyrate... 

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. 

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. 

Reagents. Diallyl fumarate was obtained from Pfaltz Bauer and was used without further purification. The impure diallyl maleate (failed in hydrosilylation), trichlorosilane, and trimethylorthoformate were obtained from Aldrich. Distilled DAM was obtained from Bimax Corp. and was utilized without additional treatment. Platinum catalysts and solvents were obtained internally from GE Silicones. All reactions were run under a nitrogen atmosphere. 

CP Cellulose propionate (ASTM, DIN, ISO, DAF Diallyl fumarate (ASTM)... 

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