Novel Thermosets from the Cationic Copolymerization of Modified Linseed Oils and Dicyclopentadiene

Abstract

A series of soft to tough copolymers have been prepared by the cationic copolymerization of the modified linseed oils Dilulin or ML189 with DCPD. Soxhlet extraction and solid‐state 13C NMR spectra indicate that the bulk copolymers consist of a cross‐linked oil/DCPD network interpenetrated with certain amounts of soluble components. The Tgs of the resulting Dil/DCPD and ML189/DCPD copolymers are in the range 15–83 and 8–77 °C, respectively, and increase linearly with the increase of the DCPD amount. The room‐temperature storage moduli range from 4.43 × 106 to 1.52 × 109 Pa for the Dil/DCPD copolymers and from 3.72 × 106 to 1.44 × 109 Pa for the ML189/DCPD copolymers.magnified image

Soybean and linseed oil‐based composites reinforced with wood flour and wood fibers

“…The Larock group at Iowa State University has focused its initial efforts in the study of bio‐based thermosets on high natural oil content (∼40–60 wt %) materials 21–24. The cationic copolymerization of modified vegetable oils and other vinylic comonomers results in homogeneous bio‐based materials with a smooth surface 25. Due to the problems associated with the cure of vegetable oil‐based systems in the presence of free radical initiators, such as the entrapment of bubbles in the resin and crack formation, free radical resins received little attention in the early stages of our research 23.…”

“…[21][22][23][24] The cationic copolymerization of modified vegetable oils and other vinylic comonomers results in homogeneous bio-based materials with a smooth surface. 25 Due to the problems associated with the cure of vegetable oil-based systems in the presence of free radical initiators, such as the entrapment of bubbles in the resin and crack formation, free radical resins received little attention in the early stages of our research. 23 The thermal copolymerization of such systems has also been investigated, but the process is not considered to be practical due to the high temperatures and long times required to obtain viable materials.…”

Dye conjugation to linseed oil by highly-effective thiol-ene coupling and subsequent esterification reactions

“…They are subsequently formulated to make thermosets by using a diluent such as styrene. Norbornene rings and cyclopentadiene rings have also been introduced into soy bean oil to make homogeneous thermosets that are commercially available as Diluin ® (Cargill Industrial Specialties) and ML189 (Archer Daniels Midland Company), respectively [29]. Further examples of thermosets made by the modification via the C=C double bond of plant oils include the introduction of hydroxyl [1], carboxyl [13], enone [30], aldehyde [31] and phosphorous-based groups [32].…”

Desenvolvimento de novas combinações monômero - catalisador para a produção de polímeros via ROMP

“…Petrovic et al desenvolveu poliuretanas que variam de macias e elásticas para duras e vítreas usando ácidos HX (X = -Br, -Cl, -CH3O) para abrir os anéis epóxidos dos óleos [24] . Wang et al preparou uma série de polióis a partir do óleo de soja epoxidado (ESBO) utilizando 1,2-etanodiol e 1,2-propanodiol para abrir os anéis epoxidado; o efeito do número de OH nesses polióis sobre as propriedades térmicas e mecânicas do molde final da poliuretana foram estudados [18,25] .…”

“…[24,26] . A ROMP é uma maneira versátil de sintetizar materiais macromoleculares, este tipo de polimerização tem sido extensivamente utilizado para preparar sistemas biorenováveis, a partir dos monômeros à base de óleos vegetais [20,[26][27][28] .…”