scholarly journals Acetoacetate Based Thermosets Prepared by Dual-Michael Addition Reactions

Polymers ◽  
2019 ◽  
Vol 11 (9) ◽  
pp. 1408 ◽  
Author(s):  
Konuray ◽  
Fernández-Francos ◽  
Ramis ◽  
Serra

A novel set of dual-curable multiacetoacetate-multiacrylate-divinyl sulfone ternary materials with versatile and manipulable properties are presented. In contrast to common dual-curing systems, the first stage polymer herein consists of a densely crosslinked, high Tg network as a result of base-catalyzed multiacetoacetate-divinyl sulfone Michael addition. A more flexible secondary network forms after base-catalyzed Michael addition of remaining multiacetoacetate to multiacrylate. Curing is truly sequential as the rates of the two Michael additions are significantly different. Curing kinetics were analyzed using differential scanning calorimetry (DSC) and Fourier-transform infrared (FTIR). The materials at each curing stage were characterized using dynamic mechanical analysis (DMA) and SEM. Although some phase separation was observed in certain formulations, the incompatibilities were minimized when the molar percentage of the acetoacetate-divinyl sulfone polymer network was above 75%. Furthermore, the environmental scanning electron microscopy (ESEM) images of these materials show that the more flexible acetoacetate-acrylate phase is dispersed in the form of polymeric spheres within the rigid acetoacetate-divinyl sulfone matrix. This unique dual microstructure can potentially render these materials highly resilient in applications requiring densely crosslinked polymer architectures with enhanced toughness.

Polymers ◽  
2019 ◽  
Vol 11 (11) ◽  
pp. 1855 ◽  
Author(s):  
Li-wu Zu ◽  
Bao-chang Gao ◽  
Zhong-cheng Pan ◽  
Jun Wang ◽  
Abdul Qadeer Dayo ◽  
...  

Phenol-diaminodiphenylmethane-based benzoxazine (P-ddm)/phthalocyanine copolymer was prepared by using P-ddm resin as matrix and 3,10,17,24-tetra-aminoethoxy lead phthalocyanine (APbPc) as additive. Fourier-transform infrared (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA) were used to investigate the curing behavior, curing kinetics, dynamic mechanical properties, thermal stability, and impact strength of the prepared copolymers. The kinetic parameters for the P-ddm/APbPc blend curing processes were examined by utilizing the iso-conversional, Flynn–Wall–Ozawa, and Málek methods. The P-ddm/APbPc blends exhibit two typical curing processes, and DSC results confirmed that the blending of APbPc monomer can effectively reduce the curing temperature of P-ddm resin. The autocatalytic models also described the non-isothermal curing reaction rate well, and the appropriate kinetic parameters of the curing process were obtained. The DMA and impact strength experiments proved that the blending of APbPc monomer can significantly improve the toughness and stiffness of P-ddm resin, the highest enhancements were observed on 25 wt.% addition of APbPc, the recorded values for the storage modulus and impact strength were 1003 MPa and 3.60 kJ/m2 higher, respectively, while a decline of 24.6 °C was observed in the glass transition temperature values. TGA curves indicated that the cured copolymers also exhibit excellent thermal stabilities.


Coatings ◽  
2020 ◽  
Vol 10 (10) ◽  
pp. 936 ◽  
Author(s):  
Ting Liu ◽  
Jingfan Wang ◽  
Fumin Chi ◽  
Zhankun Tan ◽  
Liu Liu

The effects of fennel essential oil (FEO) and peppermint essential oil (PEO) on chitosan-based films were evaluated in this study. The results showed that the addition of FEO and PEO slightly increased the density and thickness, while significantly decreasing the moisture content, water swelling, and solubility properties. The color values (L, a, b, ΔE and whiteness index (WI)) of the composite films containing FEO and PEO changed obviously with a tendency toward yellowness, which was beneficial in resisting food decomposition caused by ultraviolet light. The differential scanning calorimetry (DSC) and fourier-transform-infrared (FTIR) results indicated that the addition of FEO and PEO affected the structure of the chitosan films, while the interaction between the chitosan and polyphenols in FEO and PEO established new hydrogen bonds and improved the thermal stability. The environmental scanning electron microscopy (ESEM) illustrated that the surfaces of the composite films containing FEO and PEO were smooth, but the cross-section was rougher than in pure chitosan film. Furthermore, the composite films containing FEO and PEO exhibited prominent antioxidant activity. In short, the novel active chitosan-based films with incorporated FEO and PEO present broad application prospects in fresh-cut meat or vegetable packaging.


2012 ◽  
Vol 182-183 ◽  
pp. 104-109
Author(s):  
Cheng Long Yu ◽  
Xin Hao ◽  
Hong Tao Jiang ◽  
Li Li Wang ◽  
Zheng Guang Zhang ◽  
...  

α-Al2O3 platelets were prepared in the interface of Na2O-CaO-SiO2 glass induced by Al. Phase identification was accomplished by X-ray diffraction analysis. The morphology of the platelets was observed using an Environmental Scanning Electron Microscopy (ESEM). The changes for the mixtures of the Al powders and the glass powders that occurred during heating were characterized by a combination of differential scanning calorimetry (DSC) and thermalgravimety(TG) on a multi-functional instrument. Confirmed by XRD and ESEM, at 1200°C, the prepared platelets have mean diameters between 400nm and 1000nm. Most of them are aggregated and part of them through intergrowth. The crystals develop from the interface between glass and Al, and can form good moistening with the glass matrix. DSC/TG shows that γ-Al2O3 formed by oxidation of Al, transforms into α-Al2O3 and grow into the platelet α-Al2O3 crystals owing to the molten Al and the molten glass. On the other hand, part of the molten Al erodes into the glass and makes the deviation of the Na2O-CaO-SiO2 ternary system into Na2O-Al2O3-SiO2 ternary system, resulting in the formation of NaAlSiO4.


Coatings ◽  
2019 ◽  
Vol 9 (1) ◽  
pp. 37 ◽  
Author(s):  
Tong Wang ◽  
Jianli Wang ◽  
Xianfeng He ◽  
Zhiyuan Cao ◽  
Dongdong Xu ◽  
...  

In this work a novel ambient curable coating was synthesized based on the Michael addition reaction of acetoacetylated castor oil and a multifunctional acrylate. In the research, we used hexamethylene diacrylate as crosslinker to optimize the reaction conditions and found that a ratio of acetoacetylated castor oil to acrylate groups of 1:1.5 and a catalyst (DBU) loading of 2 wt % provided an appropriate curing time. The acetoacetylated castor oil was characterized by 1H NMR and 13C NMR spectroscopy and the obtained coating characterized by FTIR to confirm the functionalization reaction. The tensile strength, cross linking density, and thermal properties of the resulting thermosets were investigated by dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Results demonstrated that the glass transition temperatures, tensile strength, and thermal degradation were significantly improved with higher cross-linking density. Moreover, we prepared films with different multifunctional acrylate cross-linkers and found that with the increase of cross-linking density, the swelling of the film rate decreased. Overall, thermosets made from Michael crosslinking technology provided a highly bio-based coating system.


2014 ◽  
Vol 611-612 ◽  
pp. 273-279 ◽  
Author(s):  
Ismet Baran ◽  
Jesper Hattel ◽  
Remko Akkerman

In this study, a thermo-mechanical finite element model is developed to predict the spring-in of an industrially pultruded L-shaped profile made of glass/polyester composite. The resin curing kinetics are obtained from the differential scanning calorimetry (DSC) experiments. The development of the resin modulus is derived using the dynamic mechanical analysis (DMA) tests and the effective mechanical properties of the processing composite are calculated using a micromechanical model. The temperature and degree of cure distributions are obtained in a three dimensional (3D) thermo-chemical anlaysis using the finite element method (FEM). The process induced distortions are then calculated using these distributions in a 2D quasi-static mechanical analysis in which generalized plane strain elements are utilized. The predicted spring-in pattern at the end of the process is found to agree quite well with the one observed for the real pultruded parts in a commercial pultrusion company. In addition, the effects of the pulling speed and the part thickness on the spring-in formations are investigated using the proposed numerical simulation tool. It is found that the magnitude of the spring-in increases with an increase in the pulling speed and part thickness.


Author(s):  
Howard S. Kaufman ◽  
Keith D. Lillemoe ◽  
John T. Mastovich ◽  
Henry A. Pitt

Gallstones contain precipitated cholesterol, calcium salts, and proteins. Calcium (Ca) bilirubinate, palmitate, phosphate, and carbonate occurring in gallstones have variable morphologies but characteristic windowless energy dispersive x-ray (EDX) spectra. Previous studies of gallstone microstructure and composition using scanning electron microscopy (SEM) with EDX have been limited to dehydrated samples. In this state, Ca bilirubinates appear as either glassy masses, which predominate in black pigment stones, or as clusters, which are found mostly in cholesterol gallstones. The three polymorphs of Ca carbonate, calcite, vaterite, and aragonite, have been identified in gallstones by x-ray diffraction, however; the morphologies of these crystals vary in the literature. The purpose of this experiment was to study fresh gallstones by environmental SEM (ESEM) to determine if dehydration affects gallstone Ca salt morphology.Gallstones and bile were obtained fresh at cholecystectomy from 6 patients. To prevent dehydration, stones were stored in bile at 37°C. All samples were studied within 4 days of procurement.


Author(s):  
Klaus-Ruediger Peters

Environmental SEM operate at specimen chamber pressures of ∼20 torr (2.7 kPa) allowing stabilization of liquid water at room temperature, working on rugged insulators, and generation of an environmental secondary electron (ESE) signal. All signals available in conventional high vacuum instruments are also utilized in the environmental SEM, including BSE, SE, absorbed current, CL, and X-ray. In addition, the ESEM allows utilization of the flux of charge carriers as information, providing exciting new signal modes not available to BSE imaging or to conventional high vacuum SEM.In the ESEM, at low vacuum, SE electrons are collected with a “gaseous detector”. This detector collects low energy electrons (and ions) with biased wires or plates similar to those used in early high vacuum SEM for SE detection. The detector electrode can be integrated into the first PLA or positioned at any other place resulting in a versatile system that provides a variety of surface information.


Author(s):  
B. M. Culbertson ◽  
M. L. Devinev ◽  
E. C. Kao

The service performance of current dental composite materials, such as anterior and posterior restoratives and/or veneer cements, needs to be improved. As part of a comprehensive effort to find ways to improve such materials, we have launched a broad spectrum study of the physicochemical and mechanical properties of photopolymerizable or visible light cured (VLC) dental composites. The commercially available VLC materials being studied are shown in Table 1. A generic or neat resin VLC system is also being characterized by SEM and TEM, to more fully understand formulation variables and their effects on properties.At a recent dental research meeting, we reported on the differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) characterization of the materials in Table 1. It was shown by DSC and DMA that the materials are substantially undercured by commonly used VLC techniques. Post curing in an oral cavity or a dry environment at 37 to 50°C for 7 or more hours substantially enhances the cure of the materials.


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