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Concept: Thermosetting plastics


Nitrogen-based thermoset polymers have many industrial applications (for example, in composites), but are difficult to recycle or rework. We report a simple one-pot, low-temperature polycondensation between paraformaldehyde and 4,4'-oxydianiline (ODA) that forms hemiaminal dynamic covalent networks (HDCNs), which can further cyclize at high temperatures, producing poly(hexahydrotriazine)s (PHTs). Both materials are strong thermosetting polymers, and the PHTs exhibited very high Young’s moduli (up to ~14.0 gigapascals and up to 20 gigapascals when reinforced with surface-treated carbon nanotubes), excellent solvent resistance, and resistance to environmental stress cracking. However, both HDCNs and PHTs could be digested at low pH (<2) to recover the bisaniline monomers. By simply using different diamine monomers, the HDCN- and PHT-forming reactions afford extremely versatile materials platforms. For example, when poly(ethylene glycol) (PEG) diamine monomers were used to form HDCNs, elastic organogels formed that exhibited self-healing properties.

Concepts: Polymer chemistry, Monomer, Plastic, Carbon fiber, Thermoplastic, Polyethylene terephthalate, Thermosetting plastics, Thermosetting polymer


Here we report the synthesis of thermosetting resins from low molar mass Kraft lignin fractions of high functionality, re-fined by solvent extraction. Such fractions were fully characterized by 31P-NMR, 2D-HSQC NMR, SEC and DSC in order to obtain a detailed description of the structures. Reactive oxirane moieties were introduced on the lignin backbone under mild reaction conditions and quantified by simple 1H-NMR analysis. The modified fractions were chemically cross-linked with a flexible polyether diamine (Mn≈2000), in order to obtain epoxy thermosets. Epoxies from different lignin fractions, studied by DSC, DMA, tensile tests and SEM, demonstrated substantial differences in terms of thermo-mechanical prop-erties. For the first time, strong relationships between lignin structures and epoxy properties could be demonstrated. The suggested approach provides unprecedented possibilities to tune network structure and properties of thermosets based on real lignin fractions, rather than model compounds.

Concepts: Chemical reaction, Polymer chemistry, Lignin, Plastic, Thermoplastic, Kraft process, Thermosetting plastics, Thermosetting polymer


Design and direct fabrication of high-performance thermosets and composites via 3D printing are highly desirable in engineering applications. Most 3D printed thermosetting polymers to date suffer from poor mechanical properties and low printing speed. Here, a novel ink for high-speed 3D printing of high-performance epoxy thermosets via a two-stage curing approach is presented. The ink containing photocurable resin and thermally curable epoxy resin is used for the digital light processing (DLP) 3D printing. After printing, the part is thermally cured at elevated temperature to yield an interpenetrating polymer network epoxy composite, whose mechanical properties are comparable to engineering epoxy. The printing speed is accelerated by the continuous liquid interface production assisted DLP 3D printing method, achieving a printing speed as high as 216 mm h-1 . It is also demonstrated that 3D printing structural electronics can be achieved by combining the 3D printed epoxy composites with infilled silver ink in the hollow channels. The new 3D printing method via two-stage curing combines the attributes of outstanding printing speed, high resolution, low volume shrinkage, and excellent mechanical properties, and provides a new avenue to fabricate 3D thermosetting composites with excellent mechanical properties and high efficiency toward high-performance and functional applications.

Concepts: Polymer chemistry, Plastic, Composite material, Inkjet printer, Epoxy, Thermoplastic, Thermosetting plastics, Thermosetting polymer


The synthesis of polymers from renewable resources is a burning issue that is actively investigated. Polyepoxide networks constitute a major class of thermosetting polymers and are extensively used as coatings, electronic materials, adhesives. Owing to their outstanding mechanical and electrical properties, chemical resistance, adhesion, and minimal shrinkage after curing, they are used in structural applications as well. Most of these thermosets are industrially manufactured from bisphenol A (BPA), a substance that was initially synthesized as a chemical estrogen. The awareness on BPA toxicity combined with the limited availability and volatile cost of fossil resources and the non-recyclability of thermosets implies necessary changes in the field of epoxy networks. Thus, substitution of BPA has witnessed an increasing number of studies both from the academic and industrial sides. This review proposes to give an overview of the reported aromatic multifunctional epoxide building blocks synthesized from biomass or from molecules that could be obtained from transformed biomass. After a reminder of the main glycidylation routes and mechanisms and the recent knowledge on BPA toxicity and legal issues, this review will provide a brief description of the main natural sources of aromatic molecules. The different epoxy prepolymers will then be organized from simple, mono-aromatic di-epoxy, to mono-aromatic poly-epoxy, to di-aromatic di-epoxy compounds, and finally to derivatives possessing numerous aromatic rings and epoxy groups.

Concepts: DNA, Polymer chemistry, Chemical substance, Bisphenol A, Plastic, Epoxy, Thermosetting plastics, Thermosetting polymer


The work herein presented describes the synthesis and polymerization of series of biobased epoxy resins prepared through lipase catalyzed transesterification. The epoxy-functional polyester resins with various architectures (linear, tri-branched and tetra-branched) were synthesized through condensation of fatty acids derived from epoxidized soybean oil and linseed oil with 3 different hydroxyl cores under bulk conditions. The selectivity of the lipases towards esterification/ transesterification reactions allowed the formation of macromers with up to 12 epoxides in the backbone. The high degree of functionality of the resins resulted in polymer thermosets with Tg values ranging from -25 to over 100oC prepared through cationic polymerization. The determining parameters of the synthesis and the mechanism for the formation of the species were determined through kinetic studies by 1H NMR, SEC and molecular modelling studies. The correlation between macromer structure and thermoset properties was studied through real time-FTIR measurements, DSC and DMA.

Concepts: Polymer chemistry, Triglyceride, Omega-3 fatty acid, Fat, Plastic, Linoleic acid, Epoxide, Thermosetting plastics


Cyclic loading conditions are commonly encountered in the applications of shape memory polymers (SMPs), where the cyclic characteristics of the materials determine their performance during the service life, such as deformation resistance, shape recovery speed and shape recovery ratio. Recent studies indicate that in addition to the physical damage or some other irreversible softening effects, the viscoelastic nature could also be another possible reason for the degraded cyclic behavior of SMPs. In this paper, we explore in detail the influence of the viscoelastic properties on the cyclic tension and shape memory (SM) behavior of an epoxy based amorphous thermosetting polymer. Cyclic experiments were conducted first, which show that although the epoxy material does not have any visible damage or irreversible softening effect during deformation, it still exhibits obvious degradation in the cyclic tension and SM behaviors. A linear multi-branched model is utilized to assist in the prediction and understanding of the mechanical responses of amorphous SMPs. Parametric studies based on the applied model suggest that the shape memory performance can be improved by adjusting programming and recovery conditions, such as lowering the loading rate, increasing the programming temperature, and reducing the holding time.

Concepts: Psychology, Polymer chemistry, Continuum mechanics, Plastic, Materials science, Behavior, Polymers, Thermosetting plastics


In the last decades a new class of thermoset phenolic resin is emerging as a substitute of the traditional epoxy and phenolic resins in the aircraft industry. This new class is called polybenzoxazines and its associates the epoxy resin’s mechanical properties and phenolic resin’s thermal and flame retardant properties, resulting in a resin with superior properties when analyzed with the others singly. The introduction of carbon nanotubes in low concentration into polymeric matrices can produce nanostructured materials with good properties. Thus, in this study, nanostructured composites of benzoxazine resin were processed with different concentration of carbon nanotubes (0.1%, 0.5% and 1.0% w/w). In order to evaluate the thermostability of the benzoxazine resin and its nanostructured composites, it was performed a degradation kinetic study using the thermogravimetric technique. For that, the analysis have been done with the temperature ranging from 25 degrees C to 1000 degrees C at nitrogen atmosphere (100 mL x min(-1)) and in different heating rates (2, 4, 6, 8, 10 and 20 degrees C x min(-1)), in order to obtain the kinetic parameters (activation energy, E(a), and pre-exponential factor, A), based on Ozawa-Wall-Flynn model. The results showed excellent agreement between the thermogravimetric curves obtained and the Ozawa-Wall-Flynn method. The degradation kinetic study showed that the introduction of carbon nanotubes in the benzoxazine matrix does not change the thermostability of the resin, so that it does not have a significant influence in the shelf life of the material.

Concepts: Temperature, Plastic, Carbon nanotube, Composite material, Epoxy, Fiberglass, Thermosetting plastics, Synthetic resins


A new 100 % bio-based thermosetting coating system was developed from epoxidized sucrose soyate crosslinked with blocked bio-based dicarboxylic acids. A solvent-free, green method was used to block the carboxylic acid groups and render the acids miscible with the epoxy resin. The thermal reversibility of this blocking allowed for the formulation of epoxy-acid thermoset coatings that are 100 % bio-based. This was possible due to the volatility of the vinyl ethers under curing conditions. These systems have good adhesion to metal substrates and perform well under chemical and physical stress. Additionally, the hardness of the coating system is dependent on the chain length of the diacid used, making it tunable.

Concepts: Alcohol, Acetic acid, Carboxylic acid, Plastic, Block, Epoxide, Dicarboxylic acid, Thermosetting plastics


In this study, two novel colorless thermoset epoxy resins with anodically electrochromic characteristic were prepared from the thermal curing reaction of two triphenylamine-based diamine monomers, 4,4'-diamino-4'‘-methoxytriphenylamine (1) and N,N’-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-1,4-phenylenediamine (2) with aliphatic epoxy triglycidyl isocyanurate, respectively. The resulting thermoset epoxy resins showed excellent softening temperature (Ts, 270 and 280 oC) due to the rigid structure and highly crosslinking density. In addition, novel colorless epoxy resin films revealed good reversible electrochemical oxidation and interesting multi-electrochromic behavior with high contrast ratio both in the visible and NIR region. The aliphatic thermoset epoxy resins also exhibited high transparency in visible region as colorless and great potential for practical electrochromic applications.

Concepts: Plastic, Epoxy, Contrast ratio, Thermosetting plastics


Novel nanostructured unsaturated polyester resin-based thermosets, modified with poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO) and two poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) block copolymers (BCP), were developed and analyzed. The effects of molecular weights, blocks ratio and curing temperatures on the final morphology, optical and mechanical properties were reported. The block influence on the BCP miscibility was studied through uncured and cured mixtures of UP resins with PEO and PPO homopolymers having molecular weights similar to molecular weight of the blocks of BCP. The final morphology of the nanostructured thermosetting systems, containing BCP or homopolymers, was investigated and multiple mechanisms of nanostructuration were listed and explained. By considering the miscibility of the each block before and after curing, it was determined that the formation of the nanostructured matrices followed a self-assembly mechanism or a polymerization-induced phase separation mechanism. The miscibility between PEO or PPO blocks with one of two phases of UP matrix was highlighted due to its importance in the final thermoset properties. Relationships between the final morphology and thermoset optical and mechanical properties were examined. The mechanisms and physics behind the morphologies guide towards the design of highly transparent, nanostructured and toughened thermosetting UP systems.

Concepts: Polymer, Copolymer, Polymer chemistry, Plastic, Molecular mass, Thermoplastic, Thermosetting plastics, Thermosetting polymer