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We describe here the fabrication, characterization, and properties of tough bioplastics made of a babassu oil-based acrylic polymer (PBBM), hemicellulose xylan grafted with PBBM chains, and carnauba wax (CW). The plastic was primarily designed to obtain bioderived materials that can replace low-density polyethylene (LDPE) in certain food packaging applications. To obtain plastic, the radical polymerization of an original babassu oil-based acrylic monomer (BBM) in the presence of xylan macromolecules modified with maleic anhydride (X-MA) was conducted. The polymerization resulted in a material (PBBM-X) mostly consisting of highly branched PBBM/X-MA macromolecules. PBBM-X has a glass transition of 42 °C, a storage modulus of 130 MPa (at 25 °C, RT), and a Young's modulus of 30 MPa at RT. To increase the moduli, we blended PBBM-X with carnauba wax, a natural material with a high modulus and a melting temperature of ~80 °C. It was found that PBBM-X is compatible with the wax, as evidenced by the alternation of the material's thermal transitions and the co-crystallization of BBM side alkyl fragments with CW. As a result, the PBBM-X/CW blend containing 40% of the wax had a storage modulus of 475 MPa (RT) and a Young's modulus of 248 MPa (RT), which is close to that of LDPE. As polyethylene, the PBBM-X and PBBM-X/CW bioplastics have the typical stress-strain behavior demonstrated by ductile (tough) plastics. However, the bioplastic's yield strength and elongation-at-yield are considerably lower than those of LDPE. We evaluated the moisture barrier properties of the PBBM-X/(40%)CW material and found that the bioplastic's water vapor permeability (WVP) is quite close to that of LDPE. Our bioderived material demonstrates a WVP that is comparable to polyethylene terephthalate and lower than the WVP of nylon and polystyrene. Taking into account the obtained results, the fabricated materials can be considered as polyethylene alternatives to provide sustainability in plastics production in the packaging areas where LDPE currently dominates. [ABSTRACT FROM AUTHOR]

This study demonstrated that polymerization behavior of plant oil-based acrylic monomers (POBMs) synthesized in one-step transesterification reaction from naturally rich in oleic acid olive, canola, and high-oleic soybean oils is associated with a varying mass fraction of polyunsaturated fatty acid fragments (linoleic (C18:2) and linolenic (C18:3) acid esters) in plant oil. Using miniemulsion polymerization, a range of stable copolymer latexes was synthesized from 60 wt.% of each POBM and styrene to determine the impact of POBM chemical composition (polyunsaturation) on thermal and mechanical properties of the resulted polymeric materials. The unique composition of each plant oil serves as an experimental tool to determine the effect of polyunsaturated fatty acid fragments on POBM polymerization behavior and thermomechanical properties of crosslinked films made from POBM-based latexes. The obtained results show that increasing polyunsaturation in the copolymers results in an enhanced crosslink density of the latex polymer network which essentially impacts the mechanical properties of the films (both Young's modulus and toughness). Maximum toughness was observed for crosslinked latex films made from 50 wt.% of each POBM in the monomer feed. [ABSTRACT FROM AUTHOR]

In recent years, polymer chemistry has experienced an intensive development of a new field regarding the synthesis of aliphatic and aromatic biobased monomers obtained from renewable plant sources. A one-step process for the synthesis of new vinyl monomers by the reaction of direct transesterification of plant oil triglycerides with N-(hydroxyethyl)acrylamide has been recently invented to yield plant oil-based monomers (POBMs). The features of the POBM chemical structure, containing both a polar (hydrophilic) fragment capable of electrostatic interactions, and hydrophobic acyl fatty acid moieties (C15-C17) capable of van der Waals interactions, ensures the participation of the POBMs fragments of polymers in intermolecular interactions before and during polymerization. The use of the POBMs with different unsaturations in copolymerization reactions with conventional vinyl monomers allows for obtaining copolymers with enhanced hydrophobicity, provides a mechanism of internal plasticization and control of crosslinking degree. Synthesized latexes and latex polymers are promising candidates for the formation of hydrophobic polymer coatings with controlled physical and mechanical properties through the targeted control of the content of different POBM units with different degrees of unsaturation in the latex polymers. [ABSTRACT FROM AUTHOR]

(Acryloylamino)ethyl soyate is a soybean oil-based acrylic monomer (SBM) with versatile properties for applications in polymeric materials. To explore the economic feasibility of the bio-based monomers as a potential replacement for the commercial petro-counterpart, this study presents a conceptual process design and scale-up of SBMs production. Process simulation was conducted by Aspen Plus through an integrated design consisting of the catalytic transesterification conversion of soybean oil/soybean oil-based biodiesel with N-hydroxyethyl acrylamide (HEAA), followed by product recovery optimization with solvents recycling solutions. The simulation tool estimated mass and energy balances and assessed plant performance under varying process conditions (different renewable content, catalysts, soybean oil-based feedstocks, and scales). The minimum selling price (MSP) of SBM in the base case was estimated to be $78.4/kg using a cash flow analysis, which shows its economic potential compared to stearyl acrylate. The renewable content of the specialty chemical is a key technical parameter for MSP while it contributes to carbon emission reduction as well. Carbon abatement cost analysis indicates trivial economic impact of feedstock and the need for abatement consideration in different environmental profiles for bio-based chemicals. The uncertainty analysis showed the price of the fossil-based component – HEAA has the major impact on the MSP, while feedstock to HEAA ratio, tax rate, interest rate, and capital cost are sensitive parameters. Underlying areas such as wastewater treatment and economy of scale effects in producing specialty polymers were also discussed in this study. Image 1 • An integrated process of soybean oil-based monomers was designed and simulated. • TEA shows a competitive minimum selling price of $78.4/kg in the base case. • Renewable content of the specialty chemical is a key technical parameter for cost. • Carbon abatement shows the low carbon option is cheaper than business-as-usual. • Uncertainties in the price of the fossil-based component has the major impact. [ABSTRACT FROM AUTHOR]

• Monomers from plant oils copolymerized with water soluble counterparts in emulsion. • Resulted latex particle formation occurs by both micellar and homogeneous mechanism. • Emulsion copolymerization loci change when hydrophobicity of feed increases. • Aqueous solubility of POBM counterpart determines particle formation mechanism. • POBM presence is kinetically irrelevant if reactivity of counterpart radicals is high. Highly hydrophobic vinyl monomers from soybean (SBM) and olive (OVM) oil with different amounts of unsaturation were copolymerized in emulsion with significantly more soluble in water comonomers, methyl methacrylate (MMA), vinyl acetate (VA), and methyl acrylate (MA). Our intention was to demonstrate that higher aqueous solubility of the comonomer impacts the mechanism of the emulsion process by balancing latex particle homogeneous and heterogeneous (micellar) nucleation. Using an experimental method based on water insoluble dye Blue 70, it is shown that particle nucleation indeed depends to a great extent on aqueous solubility of the comonomer, along with the plant oil-based monomer (POBM) content in the feed. Upon addition of POBM into the monomer mixture with MMA (aq.solubility 1.5 wt%), the latex polymer particles originating from micellar nucleation essentially increased. In copolymerization of POBM with MA (aqueous solubility 4.9 wt%), this effect is even more pronounced. Those findings clearly indicate that copolymerization loci change when monomer feed hydrophobicity increases, and the magnitude of this effect is dependent on the comonomer aqueous solubility. Experimentally determined changes in reaction order with respect to emulsifier and initiator upon addition of POBM confirm that kinetics of emulsion copolymerization is impacted by comonomer aqueous solubility. The latter finding can be indicative of changing latex particle nucleation mode when monomer feed hydrophobicity changes. Overall, the portion of latex particles originating through micellar nucleation is higher in the copolymerization of more unsaturated SBM (with both MMA and MA) in comparison to OVM. No impact of POBM content on the reaction kinetics was observed in copolymerization with VA (aq. solubility 2.5 wt%). Here, high reactivity of growing PVA radicals in chain transfer reactions makes the presence of POBM in monomer feed kinetically irrelevant. [ABSTRACT FROM AUTHOR]

[Display omitted] • Vanillin-derived aromatic vinyl monomers undergo chain addition polymerization. • Biobased styrenes can be combined in copolymerization as conventional vinyl monomers. • Biobased aromatic vinyl monomers can act as "rigid" fragments in thermoset coatings. • Propagation coexists with intermolecular transfer to poly(3-allyl-5-vinylveratrole) Chemical structure (effect of functional substituents on vinyl bond reactivity) was used as a criterion to evaluate the (co)polymerization behavior of vanillin-derived 3-allyl-5-vinylveratrole, 4-vinylveratrole, and 2-glycidoxy-5-vinylanisole in chain-growth polymerization mechanism. After polymerization, allyl and epoxy functional groups of monomer units remain unaffected as macromolecular side groups and can be utilized in post-polymerization reactions (in particular, cross-linking). Due to the intermolecular chain transfer to polymer, a fraction of branched macromolecules can be formed in free radical polymerization of 3-allyl-5-vinylveratrole. At the same time, the kinetic study shows a similar polymerization rate for all the three investigated biobased aromatic vinyl monomers. Determined in copolymerization with methyl methacrylate Q-e values indicate that 3-allyl-5-vinylveratrole, 4-vinylveratrole and 2-glycidoxy-5-vinylanisole behave like conventional vinyl monomers and can be copolymerized interchangeably. In this manner, macromolecules with controlled amounts of cross-linkable epoxy and allyl groups incorporated into the backbone can be synthesized. Based on the glass transition temperature of the homopolymers thereof (66–93 °C), biobased aromatic vinyl monomers can serve as "rigid" macromolecular fragments and be applied in the formulation of thermoset polymer coatings. Being derived from renewable resources, 3-allyl-5-vinylveratrole, 4-vinylveratrole, and 2-glycidoxy-5-vinylanisole can be considered as a replacement for petroleum-based commodity styrene in the production of various industrial polymeric materials that utilize aromatic monomers. [ABSTRACT FROM AUTHOR]

Vinyl monomers from plant oils that have different degrees of unsaturation, soybean (SBM), and olive (OVM) oil were copolymerized in emulsion with styrene to investigate the kinetics features and feasibility of latex formation. In the presence of up to 20 wt% of SBM/OVM in the initial feed, the order of reaction with respect to the emulsifier and initiator do not depend on the plant oil-based monomers’ unsaturation degree. Reaction kinetics agree with the Smith-Ewart theory, predicting that the number of nucleated latex particles is proportional to the surfactant and initiator concentration to the powers 0.6 and 0.4, respectively. Copolymerization of styrene with plant oil-based monomers follows the typical phenomenology for emulsion polymerization of hydrophobic monomers with a micellar nucleation mechanism. Nevertheless, based on experimentally obtained latex particles’ size and number, evidence for a mixed mode of nucleation (both micellar and homogeneous) was observed in this research. Mixed nucleation can be explained by the potential surface-active properties of plant oil-based monomer molecules containing polar acryloylamino “head,” CH 2 CH C(O) NH and hydrophobic “tail,” C 17 ). Because of the effect of the degradative chain transfer on the plant oil-based monomer, the molecular weight of the resulting macromolecules decreases as the monomer degree of unsaturation and monomer fraction in the initial mixture increases. This feature can be used for controlling the molecular weight of latex polymers that come from plant oil-based monomers by varying the content and nature of bio-based monomer in feed. The thermomechanical properties of latex films depend considerably on the nature and amount of incorporated plant oil-based fragments. Their presence lowers T g (more than 40 °C difference) and provides some flexibility and toughness as compared to the normally rigid and brittle polystyrene. [ABSTRACT FROM AUTHOR]