Anomalous Thermal Characteristics of Poly(Ionic Liquids) Derived from 1-Butyl-2,3-dimethyl-4-vinylimidazolium Salts

The synthesis of 1-butyl-2,3-dimethyl-4-vinylimidazolium triflate, its polymerization, and ion exchange to yield a trio of 1-butyl-2,3-dimethyl-4-vinylimidazolium polymers is described. Irrespective of the nature of the anion, substitution at the 2-position of the imidazolium moiety substantially increases the distance between the anion and cation. The methyl substituent at the 2-position also served to expose the importance of H-bonding for the attractive potential between imidazolium moiety and anions in polymers without a methyl group at the 2-position. The thermal characteristics of poly(1-butyl-2,3-dimethyl-4-vinylimidazolium) salts and corresponding poly(1-ethyl-3-methyl-4-vinylimidazolium) salts were evaluated. While the mid-point glass transition temperatures, Tg-mid, for 1-ethyl-3-methyl-4-vinylimidazolium polymers with CF3SO3−, (CF3SO2)2N− and PF6− counterions, were 153 °C, 88 °C and 200 °C, respectively, the Tg-mid values for 1-butyl-2,3-dimethyl-4vinylimidazolium polymers with corresponding counter-ions were tightly clustered at 98 °C, 99 °C and 84 °C, respectively. This dramatically reduced influence of the anion type on the glass transition temperature was attributed to the increased distance between the center of the anions and cations in the 1-butyl-2,3-dimethyl-4-vinylimidazolium polymer set, and minimal H-bonding interactions between the respective anions and the 1-butyl-2,3-dimethyl-4-vinylimidazolium moiety. It is believed that this is the first observation of substantial independence of the glass transition of an ionic polymer on the nature of its counterion.

Study on tri-imidazole derivatives modified with triazine-trione structure as latent curing agents for epoxy resin

In this paper, four novel kinds of triazine-trione based tri-imidazole derivatives (IM-TT, 2MI-TT, 2EI-TT and EMI-TT) were synthesized through the addition reaction between triglycidyl isocyanurate (TGIC) and imidazole (IM), 2-methylimidazole (2MI), 2-ethylimidazole (2EI) and 2-ethyl-4-methylimidazole (EMI), respectively. The triazine-trione based tri-imidazole derivatives were blended with epoxy resin and the reactivity, thermal latency and thermal property were investigated. The results on curing behaviors indicated that the curing exothermic peaks of the blends with triazine-trione based tri-imidazole derivatives shifted to higher temperatures compared with those with commercial imidazoles. The curing exothermic peak temperatures (Tps) of the synthesized tri-imidazole derivatives were increased by 23–32 ℃ compared with the unmodified imidazoles. In addition, Rheological behavior results indicated that the EP blends with tri-imidazole derivatives also exhibited excellent storage stability which was as long as 38 days under room temperature. Last but not the least, the EP blends with triazine-trione based tri-imidazole derivatives also exhibited high glass transition temperatures due to introducing of triazine-trione structures with high crosslinking density. The glass transition temperatures (Tgs) of the prepared thermosets ranged from 128 to 152 ℃. The triazine-trione based tri-imidazole derivatives provide a way to prepare latency epoxy resin with high high glass transition temperature and long storage stability. Article Highlights Four novel kinds of triazine-trione based tri-imidazole derivatives were synthesized. The EP cured with the tri-imidazole derivatives displayed great thermostability. The EP cured with the tri-imidazole derivatives exhibited long storage stability.

Synthesis of novel poly(arylene ether amide) containing aliphatic ring for optical property

In this work, the monomer N, N′-bis(4-fluorobenzamide)dicyclohexyl methane (BFDCM) was synthesized successfully by 4-fluorobenzoylchloride and 4,4′-diaminodicyclohexylmethane through interfacial reaction, and then the monomer BFDCM and 1,4-benzenediol (HQ) or 4.4′-biphenol (BH) were used to prepare the novel poly(arylene ether amide) (HQ-BFDCM and BH-BFDCM) containing an aliphatic ring in the main chain by nucleophilic substitution in NMP solution. These two polymers exhibited the inherent viscosities ranging from 0.828 to 1.044 dL g−1, high glass-transition temperatures (Tg) of 214.1–235.0 °C, and weight-loss temperature (T5%) of 425.2–441.3 °C. The polymers HQ-BFDCM and BH-BFDCM could completely or partly dissolve in some polar solutions, such as NMP, DMF, and so on, and they showed moderate corrosion resistance. Additionally, the obtained polymers HQ-BFDCM and BH-BFDCM exhibited good optical property, and the optical transmittances of HQ-BFDCM and BH-BFDCM were 74% and 80% at 450 nm, respectively, which showed that they could be applied to the heat-resistant optical films.

Novel poly(arylene ether nitrile) containing pendant aliphtatic ring in the chain: Synthesis and properties

Two kinds of novel poly(arylene ether nitrile)s (CPDP-DCBN and CHDP-DCBN) containing pendant aliphtatic ring were synthesized by 4,4′-cyclopentane-1,1′-diyldiphenol (CPDP) or 4,4′-cyclohexane-1,1′-diyldiphenol (CHDP) and 2,6-dichlorobenzonitrile (DCBN) in this work. The inherent viscosities of poly(arylene ether nitrile)s (PENs) were in the range of 0.701–0.806 dL g−1. The polymers showed high glass transition temperatures ( T g) of 185.4–196.4°C and weight-loss temperatures ( T5%) of 447.8–454.3°C. The obtained CPDP-DCBN and CHDP-DCBN could be hot pressed into the films, which showed the tensile strengths of 82.6 MPa and 86.8 MPa, respectively. And the storage modulus of CPDP-DCBN and CHDP-DCBN were about 1.0 GPa and 1.5 GPa at 150°C, respectively. Additionally, the PENs could be dissolved in many solutions at room temperature, such as NMP and concentrated H2SO4, indicating that they had good solubility; they can be processed by the solution method. Meanwhile, the optical transmittance of CPDP-DCBN was 78.1% at 450 nm; it has potential to be applied to the heat-resistant optical film.

Studying the Effect of Chondroitin Sulfate on the Physicochemical Properties of Novel Gelatin/Chitosan Biopolymer-Based Cryogels

The application of biopolymers in tissue engineering is of a great interest due to of their inherent properties such as cell adhesion, biodegradation, bioavailability, and viscoelasticity. In this study, we synthesized cryogels based on biopolymers of gelatin, chitosan, and chondroitin sulfate by cryopolymerization and studied the effect of chondroitin sulfate on changing the physicochemical properties of cryogels such as pore size, pore volume, density, gel fraction, and biodegradation. A macroporous surface of the synthesized polymers has been investigated by SEM. The glass transition temperatures of the crosslinked cryogels, determined by the DSC method, were higher compared to that of the non-crosslinked cryogel used as a reference. The results of the MTT test showed that aqueous extracts of the prepared cryogels had no toxic effect on rat adipose-derived mesenchymal stem cells. The research in this area is of great importance and provides new insights into novel, effective methods for obtaining biopolymers that can be used as carriers of cells.

Sustainable polyesters via direct functionalization of lignocellulosic sugars

The development of sustainable plastics from abundant renewable feedstocks has been limited by the complexity and efficiency of their production as well as their lack of competitive material properties. Here, we demonstrate the direct transformation of the hemicellulosic fraction of non-edible biomass into a diester plastic precursor at 83% yield (95% from commercial xylose) during integrated plant fractionation with glyoxylic acid. Melt polycondensation of the resulting xylose-based diester with a range of aliphatic diols led to high-molecular weight amorphous polyesters with combined high glass transition temperatures, tough mechanical properties, and strong gas barriers, which could be processed by injection-molding, thermoforming, and 3D-printing. These polyesters could then be chemically recycled from mixed plastic waste streams or digested under biologically relevant conditions. The transformation’s simplicity led to projected costs that were competitive with fossil alternatives and significantly reduced associated greenhouse gas emissions, especially if glyoxylic acid was sourced from CO2.