139 research outputs found

    Thermal properties comparison of hybrid CF/FF and BF/FF cyanate ester-based composites

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    [EN] Insights within thermal expansion, conductivity, and decomposition dependencies with temperature on symmetrical and unsymmetrical layered carbon (CF) or basalt (BF) fabrics in combination with flax fibers (FF) were approached. Driven by commercial application and environmental concerns, the paper draws attention on a modified formula of cyanate ester with a common epoxy resin under an optimized ratio of 70:30 (vol%) as well as on the hybrid reinforcements stacking sequences. Synergetic effects were debated in terms of the CF and BF stacking sequences and corresponding volume fraction followed by comparisons with values predicted by the deployment of hybrid mixtures rules (RoHM/iRoHM). CF hybrid architectures revealed enhanced effective thermophysical properties over their BF counterparts and both over the FF-reinforced polymer composite considered as a reference. Thermal conductivities spread between 0.116 and 0.299 W m-1 K-1 from room temperature up to 250 C on all hybrid specimens, giving rise to an insulator character. Concerning the coefficient of thermal expansion, CF hybrid architectures disclosed values of 1.236 10-6 K-1 and 3.102 10-6 K-1 compared with BF affine exhibiting 4.794 10-6 K-1 and 6.245 10-6 K-1, respectively, with an increase in their volume fraction.The corresponding author gratefully acknowledges the financial assistance of German Academic Exchange Service-DAAD that enabled and supported the internship with Fraunhofer Research Institution for Polymeric Materials and Composites-PYCO, Germany. Many thanks go to Dr. Christian Dreyer and Dr. Maciej Gwiazda for the resin formula and access to the composite manufacturing technology.Motoc, DL.; Ferrándiz Bou, S.; Balart, R. (2018). Thermal properties comparison of hybrid CF/FF and BF/FF cyanate ester-based composites. 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    A renewable approach to thermosetting resins

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    10.1016/j.reactfunctpolym.2012.03.015This is a review of recent developments of thermostable resins derived basically from vegetable oils. Natural vegetable oils have been transformed in polymers following three main routes. The first is the direct polymerization through the double bonds of the fatty acid chain. The cationic copolymerization of soybean oil with styrene, divinylbenzene and different amounts of styrenic monomers containing Si, B and P has been used to produce materials with improved flame retardant properties. The second route is the functionalization of the triglyceride double bonds to introduce readily polymerizable groups: The singlet oxygen photoperoxidation of the allylic positions of high oleic sunflower oil has been used to produce hydroperoxide-containing triglycerides that were dehydrated or reduced to produce respectively enone- and hydroxyl-containing triglycerides. The enone containing derivative has been chemically crosslinked with aromatic diamines through aza-Michael reactions leading to quinoline containing thermosets. The hydroxyl-containing triglycerides have been crosslinked radically prior the introduction of acrylate groups to produce conventional and flame retardant acrylate resins. The third route explored consists of using plant oil-derived chemicals like 10-undecenoic and oleic acids to produce tailor made monomers. Acyclic diene metathesis (ADMET) polymerization has been applied to prepare a set of thermosetting polyesters with flame retardant properties. Moreover thiol-ene 'click' coupling has been used to prepare carboxylic monomers that have been explored to produce thermosetting polyanhydrides for fast drug delivery systems. A set of tailored polyols from the products of coordinative polymerization of the methyl epoxyoleate and the cationic ring opening polymer

    Solvent Choice Differentiates SET-LRP and Cu-Mediated Radical Polymerization with Non-First-Order Kinetics

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    In order to assess the role of the solvent mediating the disproportionation of Cu(I)X into Cu(0) and Cu(II)X2 during SET-LRP, a series of polymerizations of methyl acrylate initiated with methyl 2-bromopropionate and catalyzed by Cu(0)/Me6-TREN at 25 °C in DMSO, MeCN, and their mixtures were investigated. These polymerizations proceed in a dissimilar manner. SET-LRP of MA in DMSO, a solvent that mediates disproportionation, was exemplary of “ultrafast living radical polymerization” with complete conversion in 45 min following the expected first-order kinetics and providing perfect fidelity of the structure of the polymer chain ends. When the polymerization was performed in MeCN, a solvent in which Cu(I)X species do not disproportionate, it displayed nonlinear first-order kinetics with a poor retention of the bromine chain end functionality. The lack of first-order kinetics and decrease of chain end functionality with conversion indicate a nonliving polymerization in MeCN. Increasing the concentration of DMSO in DMSO/MeCN mixtures provided a continuous transition from a nonliving to a living polymerization. The incompatibility of MeCN with SET-LRP lends support that disproportionation of Cu(I)X/N ligand to Cu(0) and Cu(II)X2/N ligand is the key step in SET-LRP

    Self-Foaming Diphenolic Acid Benzoxazine

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    10.1016/j.polymer.2012.05.044This work concerns the investigation of porous polybenzoxazines based on the non-toxic renewable diphenolic acid. The approach described relies on the in situ generation of foaming agent (CO2) during the thermal curing. For this purpose, the previously synthesized benzoxazine monomer from diphenolic acid was thermally polymerized at different temperatures. As the beginning of decarboxylation is about 200 °C, we selected five foaming temperatures (Tf) ranging from 190 to 230 °C. The influence of the foaming temperature on the cellular structure and its dependency on final properties is discussed

    Polyketoesters from oleic acid. Synthesis and functionalization

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    10.1039/c3gc41346bIn this study, we exploited the reactivity of the methyl oleate enone derivative for the conversion of this renewable raw material to ketone-containing hydroxyesters. The radical-mediated thiolÂżene addition to the conjugated double bonds has been investigated and low yields were obtained due to secondary reactions. The thiol-Michael addition under acidic and basic/nucleophilic conditions was also examined. While using vanadyl triflate (VO(OTf)2), a slight excess of thiol was necessary to complete the reaction, by using both basic/nucleophilic catalysts 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), quantitative conversion was achieved under stoichiometric conditions in shorter reaction times. The obtained hydroxyester, carrying sulphide and ketone functional groups, was used to obtain polyesters by Novozyme-435 enzymatic polymerization. The coupling between the ketone group of the repeating unit and a model oxyamine has been used to demonstrate the polyketoester functionalization via oxime formation

    Flame Retardant High Oleic Sunflower Oil-Based Thermosetting Resins Through Aza- and Phospha-Michael Additions

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    10.1002/pola.26562A novel phosphorus-containing vegetable oil (PETR) was prepared through phospha-Michael addition of a diphenyl phosphine oxide to the enone derivative of high-oleic sunflower oil (ETR). The reaction was investigated using the enone derivative of methyl oleate under conventional thermal heating and microwave irradiation. The kinetic study showed a great enhancement of reaction rate for the microwave-initiated addition. The crosslinking of ETR with diaminodiphenylmethane (DDM) via aza-Michael addition was also investigated under microwave irradiation, showing a noticeable acceleration of the curing. The new phosphorus-containing triglyceride was crosslinked with DDM to obtain phosphorus-containing vegetable oil-based thermosets of different phosphorus contents. Limiting oxygen index values from 26.4 to 35.0 for the final materials were obtained, demonstrating that the flame retardant properties of vegetable oil-based thermosets can be improved by adding covalently bonded phosphorus to the polyme

    Vinylsulfide-containing polyesters and copolyesters from fatty acids: Thiol-yne monomer synthesis and thiol-ene functionalization

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    10.1002/macp.201400191The synthesis of a vinylsulfide-containing hydroxy acid (VSHA) from undecylenic fatty acid via thiol-yne monoaddition is described. Metal- and enzymatic-catalyzed polycondensation of VSHA is investigated to obtain functional polyesters with a view to further modification. Higher molecular weights are obtained when using enzymatic polymerization. Random copolymers are prepared by direct enzymatic copolymerization of VSHA and e-caprolactone (CL) and triblock CL-VSHA-CL copolymers are obtained by consecutive VSHA self-condensation and ring-opening polymerization. The copolymers display semicrystalline behavior and a good thermal stability with no significant weight loss below 300 °C. Thiol-ene chemistry-type crosslinking and surface functionalization are employed to open new application fields. Evidence of the successful reactions is obtained by NMR, IR, and fluorescence measurements
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