scholarly journals Effects of End-Caps on the Atropisomerization, Polymerization, and the Thermal Properties of ortho-Imide Functional Benzoxazines

Polymers ◽  
2019 ◽  
Vol 11 (3) ◽  
pp. 399 ◽  
Author(s):  
Kan Zhang ◽  
Yuqi Liu ◽  
Zhikun Shang ◽  
Corey Evans ◽  
Shengfu Yang
Keyword(s):  
Thermal Properties ◽  
Density Functional ◽  
Structural Information ◽  
Steric Structure ◽  
Polymerization Process ◽  
Scanning Calorimetry ◽  
Thermally Activated ◽  
13C Nuclear Magnetic Resonance ◽  
Oxazine Ring ◽  
End Caps

A new type of atropisomerism has recently been discovered in 1,3-benzoxazines, where the intramolecular repulsion between negatively charged oxygen atoms on the imide and the oxazine ring hinders the rotation about the C–N bond. The imide group offers a high degree of flexibility for functionalization, allowing a variety of functional groups to be attached, and producing different types of end-caps. In this work, the effects of end-caps on the atropisomerism, thermally activated polymerization of ortho-imide functional benzoxazines, and the associated properties of polybenzoxazines have been systematically investigated. Several end-caps, with different electronic characteristics and rigidities, were designed. 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) calculations were employed to obtain structural information, and differential scanning calorimetry (DSC) and in situ Fourier transform infrared (FT-IR) spectroscopy were also performed to study the thermally activated polymerization process of benzoxazine monomers. We demonstrated that the atropisomerization can be switched on/off by the manipulation of the steric structure of the end-caps, and polymerization behaviors can be well-controlled by the electronic properties of the end-caps. Moreover, a trade-off effect were found between the thermal properties and the rigidity of the end-caps in polybenzoxazines.

scholarly journals Resin Transfer Moldable Fluorinated Phenylethynyl-Terminated Imide Oligomers with High Tg: Structure–Melt Stability Relationship

Polymers ◽  
2021 ◽  
Vol 13 (6) ◽  
pp. 903
Author(s):  
Weijie Hong ◽  
Lili Yuan ◽  
Yanping Ma ◽  
Chao Cui ◽  
Haoyang Zhang ◽  
...  
Keyword(s):  
Glass Transition ◽  
Density Functional ◽  
Resin Transfer Molding ◽  
Cure Kinetics ◽  
Processing Temperature ◽  
Scanning Calorimetry ◽  
Transfer Molding ◽  
13C Nuclear Magnetic Resonance ◽  
Nmr Characterization ◽  
Tg Structure

Phenylethynyl-terminated aromatic polyimides meet requirements of resin transfer molding (RTM) and exhibits high glass transition temperature (Tg) were prepared. Moreover, the relationship between the polyimide backbones structure and their melting stability was investigated. The phenylethynyl-terminated polyimides were based on 4,4’-(hexafluorosiopropylidene)-diphthalic anhydride (6FDA) and different diamines of 3,4’-oxydianiline (3,4’-ODA), m-phenylenediamine (m-PDA) and 2,2’-bis(trifluoromethyl)benzidine (TFDB) were prepared. These oligoimides exhibit excellent melting flowability with wide processing temperature window and low minimum melt viscosities (< 1 Pa·s). Two of the oligoimides display good melting stability at 280–290 °C, which meet the requirements of resin transfer molding (RTM) process. After thermally cured, all resins show high glass transition temperatures (Tgs, 363–391 °C) and good tensile strength (51–66 MPa). The cure kinetics studied by the differential scanning calorimetry (DSC), 13C nuclear magnetic resonance (13C NMR) characterization and density functional theory (DFT) definitely confirmed that the electron-withdrawing ability of oligoimide backbone can tremendously affect the curing reactivity of terminated phenylethynyl groups. The replacement of 3,4’-ODA units by m-PDA or TFDB units increase the electron-withdrawing ability of the backbone, which increase the curing rate of terminated phenylethynyl groups at processing temperatures, hence results in the worse melting stability.

Electron microscopy and diffraction of crystalline dendrimers and macrocycles

1993 ◽  
Vol 51 ◽  
pp. 1218-1219
Author(s):  
C. J. Buchko ◽  
P. M. Wilson ◽  
Z. Xu ◽  
J. Zhang ◽  
S. Lee ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Liquid Crystalline ◽  
Structural Information ◽  
High Resolution Electron Microscopy ◽  
Scanning Calorimetry ◽  
Tertiary Butyl ◽  
Phenyl Acetylene ◽  
Selected Area Electron Diffraction ◽  
Liquid Crystalline Phases ◽  
Resolution Electron

The synthesis of well-defined organic molecules with unique geometries opens new opportunities for understanding and controlling the organization of condensed matter. Here, we study dendrimers and macrocycles which are synthesized from rigid phenyl-acetylene spacer units, Both units are solubilized by the presence of tertiary butyl groups located at the periphery of the molecule. These hydrocarbon materials form crystalline and liquid crystalline phases which have been studied by differential scanning calorimetry, hot stage optical microscopy, and wide-angle x-ray scattering (WAXS).The precisely defined architecture of these molecules makes it possible to investigate systematic variations in chemical architecture on the nature of microstructural organization. Here we report on the transmission electron microscopy (TEM), selected area electron diffraction (SAED), and high resolution electron microscopy (HREM) studies of crystalline thin films formed by deposition of these materials onto carbon substrates from dilute solution. Electron microscopy is very attractive for gaining structural information on new molecules due to the scarcity of material to grow single crystals suitable for conventional crystallography.

Characterization of Nostoc muscorum NCCU-442 Derived Poly-3- hydroxybutyrate (PHB) and Polyethylene Glycol (PEG) Blends

2020 ◽  
Vol 10 (3) ◽  
pp. 200-207
Author(s):  
Sabbir Ansari ◽  
Tasneem Fatma
Keyword(s):  
Thermal Properties ◽  
Polyethylene Glycol ◽  
Morphological Properties ◽  
Morphological Alteration ◽  
Nostoc Muscorum ◽  
Microbial Culture ◽  
Polymer Science ◽  
Mixed Microbial Culture ◽  
Scanning Calorimetry ◽  
Casting Technique

Background: Poly-3-hydroxybutyrate (PHB) has attracted much consideration as biodegradable biocompatible polymer. This thermoplastic polymer has comparable material properties to polypropylene. Materials with more valuable properties may result from blending, a common practice in polymer science. Objective: In this paper, blends of PHB (extracted from cyanobacterium Nostoc muscorum NCCU- 442 with polyethylene glycol (PEG) were investigated for their thermal, tensile, hydrophilic and biodegradation properties. Methods: Blends were prepared in different proportions of PHB/PEG viz. 100/0, 98/2, 95/5, 90/10, 80/20, and 70/30 (wt %) using solvent casting technique. Morphological properties were investigated by using Scanning Electron Microscopy (SEM). Differential scanning calorimetry and thermogravimetric analysis were done for thermal properties determination whereas the mechanical and hydrophilic properties of the blends were studied by means of an automated material testing system and contact angle analyser respectively. Biodegradability potential of the blended films was tested as percent weight loss by mixed microbial culture within 60 days. Results: The blends showed good misciblity between PEG and PHB, however increasing concentrations of plasticizer caused morphological alteration as evidenced by SEM micrographs. PEG addition (10 % and above) showed significant alternations in the thermal properties of the blends. Increase in the PEG content increased the elongation at break ratio i.e enhanced the required plasticity of PHB. Rate of microbial facilitated degradation of the blends was greater with increasing PEG concentrations. Conclusion: Blending with PEG increased the crucial polymeric properties of cyanobacterial PHB.

scholarly journals Improved Processing and Properties for Polyphenylene Oxide Modified by Diallyl Orthophthalate Prepolymer

Polymers ◽  
2019 ◽  
Vol 11 (12) ◽  
pp. 2016
Author(s):  
Honghua Wang ◽  
Qilin Mei ◽  
Yujie Ding ◽  
Zhixiong Huang ◽  
Minxian Shi
Keyword(s):  
Differential Scanning Calorimetry ◽  
Thermal Properties ◽  
Phase Separation ◽  
Dilution Effect ◽  
Gradual Decrease ◽  
Gel Point ◽  
Dynamic Mode ◽  
Curing Process ◽  
Scanning Calorimetry ◽  
Polyphenylene Oxide

Diallyl orthophthalate (DAOP) prepolymer was investigated as a reactive plasticizer to improve the processability of thermoplastics. The rheology of blends of DAOP prepolymer initiated by 2,3-dimethyl-2,3-diphenylbutane (DMDPB) and polyphenylene oxide (PPO) was monitored during the curing process, and their thermal properties and morphology in separated phases were also studied. Differential scanning calorimetry (DSC) results showed that the cure degree of the reactively plasticized DAOP prepolymer was reduced with increasing PPO due to the dilution effect. The increasing amount of the DAOP prepolymer led to a gradual decrease in the viscosity of the blends and the rheology behavior was consistent with the chemical gelation of DAOP prepolymer in blends. This indicated that the addition of the DAOP prepolymer effectively improved processability. The phase separation occurring during curing of the blend and the transition from the static to dynamic mode significantly influences the development of the morphology of the blend corresponding to limited evolution of the conversion around the gel point.

Mechanical and thermal characterization of grafted PP-NCC nanocomposites

2019 ◽  
pp. 089270571987822
Author(s):  
Saud Aldajah ◽  
Mohammad Y Al-Haik ◽  
Waseem Siddique ◽  
Mohammad M Kabir ◽  
Yousef Haik
Keyword(s):  
Thermal Properties ◽  
Interfacial Adhesion ◽  
Thermal Characterization ◽  
Mechanical And Thermal Properties ◽  
Screw Extruder ◽  
Scanning Calorimetry ◽  
Three Point Bending ◽  
Twin Screw ◽  
Thermal Stability Of

This study reveals the enhancement of mechanical and thermal properties of maleic anhydride-grafted polypropylene (PP- g-MA) with the addition of nanocrystalline cellulose (NCC). A nanocomposite was manufactured by blending various percentages of PP, MA, and NCC nanoparticles by means of a twin-screw extruder. The influence of varying the percentages of NCC on the mechanical and thermal behavior of the nanocomposite was studied by performing three-point bending, nanoindentation, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and Fourier-transform infrared (FTIR) spectroscopy tests. The novelty of this study stems on the NCC nanoparticles and their ability to enhance the mechanical and thermal properties of PP. Three-point bending and nanoindentation tests revealed improvement in the mechanical properties in terms of strength, modulus, and hardness of the PP- g-MA nanocomposites as the addition of NCC increased. SEM showed homogeneity between the mixtures which proved the presence of interfacial adhesion between the PP- g-MA incorporated with NCC nanoparticles that was confirmed by the FTIR results. DSC and TGA measurements showed that the thermal stability of the nanocomposites was not compromised due to the addition of the coupling agent and reinforced nanoparticles.

scholarly journals PEG-POSS Star Molecules Blended in Polyurethane with Flexible Hard Segments: Morphology and Dynamics

Molecules ◽  
2020 ◽  
Vol 26 (1) ◽  
pp. 99
Author(s):  
Konstantinos N. Raftopoulos ◽  
Edyta Hebda ◽  
Anna Grzybowska ◽  
Panagiotis A. Klonos ◽  
Apostolos Kyritsis ◽  
...  
Keyword(s):  
Glass Transition ◽  
Star Polymer ◽  
Polymerization Process ◽  
Degree Of Crystallinity ◽  
Dielectric Relaxation Spectroscopy ◽  
Scanning Calorimetry ◽  
Similar System ◽  
Soft Phase ◽  
Hard Segments ◽  
Star Molecules

A star polymer with a polyhedral oligomeric silsesquioxanne (POSS) core and poly(ethylene glycol) (PEG) vertex groups is incorporated in a polyurethane with flexible hard segments in-situ during the polymerization process. The blends are studied in terms of morphology, molecular dynamics, and charge mobility. The methods utilized for this purpose are scanning electron and atomic force microscopies (SEM, AFM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and to a larger extent dielectric relaxation spectroscopy (DRS). It is found that POSS reduces the degree of crystallinity of the hard segments. Contrary to what was observed in a similar system with POSS pendent along the main chain, soft phase calorimetric glass transition temperature drops as a result of plasticization, and homogenization of the soft phase by the star molecules. The dynamic glass transition though, remains practically unaffected, and a hypothesis is formed to resolve the discrepancy, based on the assumption of different thermal and dielectric responses of slow and fast modes of the system. A relaxation α′, slower than the bulky segmental α and common in polyurethanes, appears here too. A detailed analysis of dielectric spectra provides some evidence that this relaxation has cooperative character. An additional relaxation g, which is not commonly observed, accompanies the Maxwell Wagner Sillars interfacial polarization process, and has dynamics similar to it. POSS is found to introduce conductivity and possibly alter its mechanism. The study points out that different architectures of incorporation of POSS in polyurethane affect its physical properties by different mechanisms.

scholarly journals Demonstration of Phase Change Thermal Energy Storage in Zinc Oxide Microencapsulated Sodium Nitrate

2021 ◽  
Vol 11 (13) ◽  
pp. 6234
Author(s):  
Ciprian Neagoe ◽  
Ioan Albert Tudor ◽  
Cristina Florentina Ciobota ◽  
Cristian Bogdanescu ◽  
Paul Stanciu ◽  
...  
Keyword(s):  
Zinc Oxide ◽  
Thermal Properties ◽  
High Temperature ◽  
Energy Storage ◽  
Phase Change ◽  
Thermal Energy ◽  
Sodium Nitrate ◽  
Thermal Energy Storage ◽  
Metal Corrosion ◽  
Scanning Calorimetry

Microencapsulation of sodium nitrate (NaNO3) as phase change material for high temperature thermal energy storage aims to reduce costs related to metal corrosion in storage tanks. The goal of this work was to test in a prototype thermal energy storage tank (16.7 L internal volume) the thermal properties of NaNO3 microencapsulated in zinc oxide shells, and estimate the potential of NaNO3–ZnO microcapsules for thermal storage applications. A fast and scalable microencapsulation procedure was developed, a flow calorimetry method was adapted, and a template document created to perform tank thermal transfer simulation by the finite element method (FEM) was set in Microsoft Excel. Differential scanning calorimetry (DSC) and transient plane source (TPS) methods were used to measure, in small samples, the temperature dependency of melting/solidification heat, specific heat, and thermal conductivity of the NaNO3–ZnO microcapsules. Scanning electron microscopy (SEM) and chemical analysis demonstrated the stability of microcapsules over multiple tank charge–discharge cycles. The energy stored as latent heat is available for a temperature interval from 303 to 285 °C, corresponding to onset–offset for NaNO3 solidification. Charge–self-discharge experiments on the pilot tank showed that the amount of thermal energy stored in this interval largely corresponds to the NaNO3 content of the microcapsules; the high temperature energy density of microcapsules is estimated in the range from 145 to 179 MJ/m3. Comparison between real tank experiments and FEM simulations demonstrated that DSC and TPS laboratory measurements on microcapsule thermal properties may reliably be used to design applications for thermal energy storage.

scholarly journals Solution-Processed OLEDs Based on Thermally Activated Delayed Fluorescence Copper(I) Complexes with Intraligand Charge-Transfer Excited State

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1125
Author(s):  
Teng Teng ◽  
Jinfan Xiong ◽  
Gang Cheng ◽  
Changjiang Zhou ◽  
Xialei Lv ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Density Functional ◽  
Delayed Fluorescence ◽  
Quantum Yields ◽  
Functional Theory ◽  
Solution Processed ◽  
Thermally Activated Delayed Fluorescence ◽  
Light Emitting ◽  
Thermally Activated ◽  
Wide Range

A new series of tetrahedral heteroleptic copper(I) complexes exhibiting efficient thermally-activated delayed fluorescence (TADF) in green to orange electromagnetic spectral regions has been developed by using D-A type N^N ligand and P^P ligands. Their structures, electrochemical, photophysical, and electroluminescence properties have been characterized. The complexes exhibit high photoluminescence quantum yields (PLQYs) of up to 0.71 at room temperature in doped film and the lifetimes are in a wide range of 4.3–24.1 μs. Density functional theory (DFT) calculations on the complexes reveal the lowest-lying intraligand charge-transfer excited states that are localized on the N^N ligands. Solution-processed organic light emitting diodes (OLEDs) based on one of the new emitters show a maximum external quantum efficiency (EQE) of 7.96%.

Thermal properties of polybenzoxazine exhibiting improved toughness: Blending with cyclodextrin and its derivatives

2021 ◽  
pp. 095400832110130
Author(s):  
Hailong Li ◽  
Sipei Zhao ◽  
Li Pei ◽  
Zihe Qiao ◽  
Ding Han ◽  
...  
Keyword(s):  
Thermal Properties ◽  
Hydrogen Bonds ◽  
High Performance ◽  
Practical Application ◽  
Scanning Calorimetry ◽  
Thermoset Resins ◽  
Chemical Structures ◽  
Microscopy Techniques ◽  
Fractured Surface ◽  
Scanning Electron

Polybenzoxazines are emerging as a class of high-performance thermoset polymers that can find their applications in various fields. However, its practical application is limited by its low toughness. The cyclic β-cyclodextrin and a newly synthesized derivative (β-cyclodextrin-MAH) were separately blended with benzoxazine to improve the toughness of polybenzoxazine. The results revealed that the maximum impact strength of the blend was 12.24 kJ·m−2 and 14.29 kJ·m−2 when 1 wt.% of β-Cyclodextrin and β-Cyclodextrin-MAH, respectively, were used. The strengths were 53% and 86% higher than that of pure polybenzoxazine. The curing reaction, possible chemical structures, and fractured surface were examined using differential scanning calorimetry, Fourier transform infrared spectroscopy, and scanning electron microscopy techniques to understand the mechanism of generation of toughness. The results revealed that the sea-island structure and the presence of hydrogen bonds between polybenzoxazine and β-cyclodextrin and β-cyclodextrin-MAH resulted in the generation of toughness. Furthermore, the curves generated during thermogravimetric analysis did not significantly change, revealing the good thermal properties of the system. The phase-separated structure and the hydrogen bonds present in the system can be exploited to prepare synergistically tough polybenzoxazine exhibiting excellent thermal properties. This can be a potential way of modifying the thermoset resins.

scholarly journals Preparation and Characterization of Talc Filled Thermoplastic Polyurethane/Polypropylene Blends

2014 ◽  
Vol 2014 ◽  
pp. 1-8 ◽  
Author(s):  
Emi Govorčin Bajsić ◽  
Vesna Rek ◽  
Ivana Ćosić
Keyword(s):  
Thermal Properties ◽  
Thermoplastic Polyurethane ◽  
Mechanical Analysis ◽  
Degree Of Crystallinity ◽  
Scanning Calorimetry ◽  
Polypropylene Blends ◽  
Pp Blends ◽  
The Degree Of Crystallinity ◽  
Better Than

The effect of the addition of talc on the morphology and thermal properties of blends of thermoplastic polyurethane (TPU) and polypropylene (PP) was investigated. The blends of TPU and PP are incompatible because of large differences in polarities between the nonpolar crystalline PP and polar TPU and high interfacial tensions. The interaction between TPU and PP can be improved by using talc as reinforcing filler. The morphology was observed by means of scanning electron microscopy (SEM). The thermal properties of the neat polymers and unfilled and talc filled TPU/PP blends were studied by using dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The addition of talc in TPU/PP blends improved miscibility in all investigated TPU/T/PP blends. The DSC results for talc filled TPU/PP blends show that the degree of crystallinity increased, which is due to the nucleating effect induced by talc particles. The reason for the increased storage modulus of blends with the incorporation of talc is due to the improved interface between polymers and filler. According to TGA results, the addition of talc enhanced thermal stability. The homogeneity of the talc filled TPU/PP blends is better than unfilled TPU/PP blends.

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