Synthesis and polymerization of the bromoacrylated plant oil triglycerides to rigid, flame‐retardant polymers

Abstract

Simultaneous addition of bromine and acrylate to the double bonds of fatty acids in triglycerides was achieved. In the first part of the study, methyl oleate was bromoacrylated in the presence of acrylic acid and N-bromosuccinimide as a model compound for the application of the reaction to the triglycerides. Next, soybean oil and high oleic sunflower oil were bromoacrylated by using the same procedure. The products were characterized by GC, IR, 1 H-NMR, 13C-NMR, and mass spectrometry. The bromoacrylation yields for soybean oil and sunflower oil were 75 and 55%, respectively. A rigid thermoset polymer was prepared from the radical copolymerization of bromoacrylated soybean oil with styrene. The bromoacrylated sunflower oilstyrene copolymer showed semirigid properties. The crosslinked network structure of the copolymers was examined by their swelling behavior in different solvents. Glasstransition temperatures were also determined and soybean oil-based polymer and sunflower oil-based polymer showed a glass transition at 55-65 and 20 -30°C, respectively. The storage moduli of the soybean-based and sunflower-based polymers at room temperature were approximately 1.0 ϫ 10 10 and 1.1 ϫ 10 8 Pa, respectively. Photopolymerization was also carried out by using 2,2-dimethoxy-2-phenyl-acetophenone as initiator. The response of the cured polymers to the thermal energy produced by a small flame was also tested by the ignition respond index method according to ASTM D 3713-78 and was found to be 5 B at 2.00 mm.

Novel Polymeric Materials from Vegetable Oils and Vinyl Monomers: Preparation, Properties, and Applications

“…An increase in the acrylate level in the triglyceride effectively increases the cross-link density of the resulting AESO-based thermosets with and without styrene, resulting in a significant improvement in the mechanical properties. [56] Eren and Küsefog lu [57] reported the simultaneous addition of a bromine and an acrylate unit to the double bonds of fatty acids in triglycerides by using acrylic acid and N-bromosuccinimide to make bromoacrylated triglyceride oils. After copolymerization with styrene, the resulting thermosets from bromoacrylated soybean oil and bromoacrylated sunflower oil are rigid or semi-rigid plastics, whose physical properties are comparable to those of AESO-ST thermosets.…”

Vegetable oils as platform chemicals for polymer synthesis

“…Most of the flame retardant resins used in industry come from petroleum-based chemicals. Eren and Kusefoglu [10] reported the synthesis and characterization of flame-retardant polymers from bromoacrylated plant oil triglycerides. However, the flame-retardant resins that contain bromine release hydrogen bromide during combustion, which causes corrosion and toxicity.…”

Synthesis and characterization of cast resin based on different saturation epoxidized soybean oil

“…One of the most notable examples of this research has been the discovery of methods for producing polyols from soybean oil [14]. For example, soybean oil has double bonds (iodine number 142), but it does not give homo-or co-polymers by radical-initiated polymerization [3]. Therefore, to be useful as a monomer for free radical polymerization, the triglyceride molecule has to be suitably functionalized [3,6,8,15].…”

“…For example, soybean oil has double bonds (iodine number 142), but it does not give homo-or co-polymers by radical-initiated polymerization [3]. Therefore, to be useful as a monomer for free radical polymerization, the triglyceride molecule has to be suitably functionalized [3,6,8,15]. Many ways of modifying soybean oil have been explored, including maleinization [16], epoxidation [17,18], acrylation [19][20][21], and hydroxymethylation [22].…”