Copolymerization of a Bisphenol a Derivative and Elemental Sulfur by the RASP Process

Fossil fuel refining produces over 70 Mt of excess sulfur annually from for which there is currently no practical use. Recently, methods to convert waste sulfur to recyclable and biodegradable polymers have been delineated. In this report, a commercial bisphenol A (BPA) derivative, 2,2′,5,5′-tetrabromo(bisphenol A) (Br4BPA), is explored as a potential organic monomer for copolymerization with elemental sulfur by RASP (radical-induced aryl halide-sulfur polymerization). Resultant copolymers, BASx (x = wt% sulfur in the monomer feed, screened for values of 80, 85, 90, and 95) were characterized by thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. Analysis of early stage reaction products and depolymerization products support proposed S–Caryl bond formation and regiochemistry, while fractionation of BASx reveals a sulfur rank of 3–6. Copolymers having less organic cross-linker (5 or 10 wt%) in the monomer feed were thermoplastics, whereas thermosets were accomplished when 15 or 20 wt% of organic cross-linker was used. The flexural strengths of the thermally processable samples (>3.4 MPa and >4.7 for BAS95 and BAS90, respectively) were quite high compared to those of familiar building materials such as portland cement (3.7 MPa). Furthermore, copolymer BAS90 proved quite resistant to degradation by oxidizing organic acid, maintaining its full flexural strength after soaking in 0.5 M H2SO4 for 24 h. BAS90 could also be remelted and recast into shapes over many cycles without any loss of mechanical strength. This study on the effect of monomer ratio on properties of materials prepared by RASP of small molecular aryl halides confirms that highly cross-linked materials with varying physical and mechanical properties can be accessed by this protocol. This work is also an important step towards potentially upcycling BPA from plastic degradation and sulfur from fossil fuel refining.

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Ionic liquids: green solvents and reactive compounds? Reaction of tri-n-butylmethylphosphonium dimethylphosphate with elemental sulfur

Pure and Applied Chemistry ◽

10.1515/pac-2019-0804 ◽

2020 ◽

Vol 0 (0) ◽

Author(s):

Natalia Tarasova ◽

Efrem Krivoborodov ◽

Alexey Zanin ◽

Yaroslav Mezhuev

Keyword(s):

Ionic Liquids ◽

Nmr Spectroscopy ◽

Oxygen Atom ◽

Elemental Sulfur ◽

Green Solvents ◽

Reaction Products ◽

Mechanism Of Interaction

AbstractThe opening of the S8 ring with the formation of linear sulfur oligomers in the presence of tri-n-butylmethylphosphonium dimethylphosphate is shown. The reaction products are separated and characterized with 1H, 13C, 31P, 17O NMR spectroscopy, HD-MS, MALDI spectroscopy and XRD. It is shown that dimethylphosphate-anion is active in the reaction, and the addition of sulfur atoms occurs via the oxygen atom of dimethylphosphate-anion. It is found that a mixture of products is formed, which differ in the number of sulfur atoms in the chain. The assumptions were made about the mechanism of interaction of sulfur with tri-n-butylmethylphosphonium dimethylphosphate.

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Integration of BIM and LCA: Evaluating the environmental impacts of building materials at an early stage of designing a typical office building

Journal of Building Engineering ◽

10.1016/j.jobe.2017.10.005 ◽

2017 ◽

Vol 14 ◽

pp. 115-126 ◽

Cited By ~ 51

Author(s):

Mohammad Najjar ◽

Karoline Figueiredo ◽

Mariana Palumbo ◽

Assed Haddad

Keyword(s):

Environmental Impacts ◽

Building Materials ◽

Early Stage ◽

Office Building

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One-Step Simultaneous Differential Scanning Calorimetry-FTIR Microspectroscopy to Quickly Detect Continuous Pathways in the Solid-State Glucose/Asparagine Maillard Reaction

Journal of AOAC International ◽

10.5740/jaoacint.13-074 ◽

2013 ◽

Vol 96 (6) ◽

pp. 1362-1364 ◽

Cited By ~ 1

Author(s):

Deng-Fwu Hwang ◽

Tzu-Feng Hsieh ◽

Shan-Yang Lin

Keyword(s):

Differential Scanning Calorimetry ◽

Solid State ◽

Maillard Reaction ◽

Reaction Pathway ◽

Molar Ratio ◽

Maillard Reaction Products ◽

Reaction Products ◽

Scanning Calorimetry ◽

Ftir Microspectroscopy ◽

Amadori Product

Abstract The stepwise reaction pathway of the solid-state Maillard reaction between glucose (Glc) and asparagine (Asn) was investigated using simultaneous differential scanning calorimetry (DSC)-FTIR microspectroscopy. The color change and FTIR spectra of Glc-Asn physical mixtures (molar ratio = 1:1) preheated to different temperatures followed by cooling were also examined. The successive reaction products such as Schiff base intermediate, Amadori product, and decarboxylated Amadori product in the solid-state Glc-Asn Maillard reaction were first simultaneously evidenced by this unique DSC-FTIR microspectroscopy. The color changed from white to yellow-brown to dark brown, and appearance of new IR peaks confirmed the formation of Maillard reaction products. The present study clearly indicates that this unique DSC-FTIR technique not only accelerates but also detects precursors and products of the Maillard reaction in real time.

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Preparation and Characterization of Green Epoxy Resin Composites and Its Use in Corrosion Resistance

Materials Science Materials Review ◽

10.18063/msmr.v0i0.948 ◽

2018 ◽

Author(s):

Abbas Hassan Faris

Keyword(s):

Bisphenol A ◽

Epoxy Resin ◽

Electrolyte Solutions ◽

Kraft Lignin ◽

Diglycidyl Ether ◽

Kraft Pulping ◽

Palm Tree ◽

Scanning Calorimetry ◽

Ft Ir ◽

Nano Titanium Dioxide

In this work, appropriate alternative for diglycidyl ether bisphenol A (DGEBA) was found to avoid the destructive effects of bisphenol A. Lignin, an aromatic compound from palm tree leaves, was used as a renewable material to synthesize a bio-based epoxy resin. Lignin extracted using Kraft pulping process. Kraft Lignin was epoxidized with epichlorohydrin in alkaline medium. Nano-titanium dioxide was used as filler with ratio of 10% to prepare the green epoxy composite. The structure of the Kraft lignin and lignin-based epoxy resin was proven via Infrared spectra (FT-IR) were recorded using solid KBr disk by testing Shimadzu (FT-IR-8300) spectrophotometer. The thermal properties of the curing process of lignin-based epoxy resin and composite were investigate using Differential scanning calorimetry (DSC) analysis. Potentiodynamic measurements data revealed that the anti-corrosion performance of the lignin based epoxy resin. The study demonstrates successful of epoxidation of Kraft lignin. In addition, lignin based eopxy resin showed effective inhibitor for carbon steel in 3.5 wt. % NaCl electrolyte solutions

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Conversion of palm oil to new sulfur-based polymer by inverse vulcanization

E3S Web of Conferences ◽

10.1051/e3sconf/202128702014 ◽

2021 ◽

Vol 287 ◽

pp. 02014

Author(s):

Amin Abbasi ◽

Mohamed Mahmoud Nasef ◽

Wan Zaireen Nisa Yahya ◽

Muhammad Moniruzzaman

Keyword(s):

Thermal Stability ◽

Differential Scanning Calorimetry ◽

Fourier Transform ◽

Thermogravimetric Analysis ◽

Palm Oil ◽

Elemental Sulfur ◽

Molten State ◽

Scanning Calorimetry ◽

Environmental Friendly ◽

Sulfur Containing

The conversion of palm oil into a sulfur-based polymer by copolymerization with sulfur powder at its molten state is herein reported. The obtained sulfur-containing polymer was characterized using Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) to demonstrate the successful conversion. The disappearance of the peaks related to vinylic groups of oil together with the appearance of a peak representing C-H rocking vibrations in the vicinity of C-S bonds confirmed the copolymerization of sulfur with oil. TGA revealed that the polymers have thermal stability up to 230°C under nitrogen and the polymers leave 10% sulfur-rich ash. DSC proved that a small amount of elemental sulfur remained unreacted in the polymer, which showed amorphous and heavily crosslinked structure resembling thermosets. These copolymers are an environmental-friendly polymeric material promoting the utilization of the abundant sulfur while also adding value to palm oil.

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Determination of elemental sulfur in phosphorous pentasulfide by temperature modulated differential scanning calorimetry

Journal of Thermal Analysis and Calorimetry ◽

10.1007/s10973-012-2627-5 ◽

2012 ◽

Vol 109 (3) ◽

pp. 1285-1290 ◽

Cited By ~ 1

Author(s):

Tina M. Adams ◽

Paul Adams

Keyword(s):

Differential Scanning Calorimetry ◽

Elemental Sulfur ◽

Scanning Calorimetry ◽

Modulated Differential Scanning Calorimetry

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Copolymerization of 4-Acetylphenyl Methacrylate with Ethyl Methacrylate: Synthesis, Characterization, Monomer Reactivity Ratios, and Thermal Properties

International Journal of Polymer Science ◽

10.1155/2014/643789 ◽

2014 ◽

Vol 2014 ◽

pp. 1-10

Author(s):

Gamze Barim ◽

Mustafa Gokhun Yayla

Keyword(s):

Thermal Stability ◽

Nonlinear Least Squares ◽

Reactivity Ratios ◽

Spectroscopic Techniques ◽

Monomer Reactivity Ratios ◽

Scanning Calorimetry ◽

Ethyl Methacrylate ◽

Wide Range ◽

Monomer Feed ◽

Copolymer Poly

Methacrylates have high glass transition temperature (Tg) values and high thermal stability. A new methacrylate copolymer, poly(4-acetylphenyl methacrylate-co-ethyl methacrylate) (APMA-co-EMA), was synthesized. The thermal behaviors of copolymers were investigated by differential scanning calorimetry and thermogravimetric analysis. They behaved as new single polymers with singleTg’s and the thermal stability of the copolymers increased with increasing 4-acetylphenyl methacrylate (APMA) fraction, leading to the manufacture of copolymers with desiredTgvalues. Structure and composition of copolymers for a wide range of monomer feed ratios were determined by Fourier transform infrared (FT-IR) and1H-nuclear magnetic resonance (1H-NMR) spectroscopic techniques. Copolymerization reactions were continued up to 40% conversions. The monomer reactivity ratios for copolymer system were determined by the Kelen-Tüdös (ra(APMA)=0.81;rb(EMA)=0.61) and extended Kelen-Tüdös (ra=0.77;rb=0.54) methods and a nonlinear least squares (ra=0.74;rb=0.49) method.

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Azomethine ether-based potential curing agent for epoxy resin (diglycidyl ether of bisphenol A): Synthesis and characterization

Journal of Elastomers & Plastics ◽

10.1177/0095244320928570 ◽

2020 ◽

pp. 009524432092857

Author(s):

Fozia Noreen ◽

Ahtaram Bibi ◽

Naila Khalid ◽

Imran Ullah Khan

Keyword(s):

Spectral Analysis ◽

Bisphenol A ◽

Light Emission ◽

Condensation Reaction ◽

Stokes Shift ◽

Green Light ◽

Diglycidyl Ether ◽

Proton Nuclear Magnetic Resonance ◽

Curing Agent ◽

Scanning Calorimetry

Novel azomethine ether-based compounds (A: N-((4-(9-(4-(phenylimino)methyl)phenoxy)nonyloxy)benzylidene)bezenamine and B: N-((4-(9-(4-(p-hydroxyphenylimino)methyl)phenoxy)nonyloxy)benzylidene)-4-hydroxybenzenamine) were synthesized by condensation reaction of dialdehyde, 4,4-(1,9-nonandiyle)bis(oxy)dibenzaldehyde with aromatic amines. Structures of synthesized compounds were successfully characterized by Fourier transform infrared (FTIR), ultraviolet–visible, proton nuclear magnetic resonance imaging and photoluminescence (PL) spectroscopy. The PL spectral analysis revealed that emission maxima of compounds A and B are at 475 and 500 nm, respectively, indicate blue and green light emission with large Stokes shift range (Δ λ ST, 109–138 nm). Two series of polymers: one azomethine-based polymers (C1–C5) and other without azomethine (H1–H4) were prepared by curing diglycidyl ether of bisphenol A with a synthesized curing agent (B) and commercial curing agent, respectively, in various proportions. The structural characterization of the resulting polymers was carried out by FTIR spectral analysis. Thermal properties revealed that azomethine-based polymers (C1–C5) were thermally stable up to 400°C as compared to H1–H4. The glass transition temperature of the polymers, determined by differential scanning calorimetry, was in the range 121–123°C.

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Use of Coal Bottom Ash and CaO-CaCl2-Activated GGBFS Binder in the Manufacturing of Artificial Fine Aggregates through Cold-Bonded Pelletization

Materials ◽

10.3390/ma13245598 ◽

2020 ◽

Vol 13 (24) ◽

pp. 5598

Author(s):

Dongho Jeon ◽

Woo Sung Yum ◽

Haemin Song ◽

Seyoon Yoon ◽

Younghoon Bae ◽

...

Keyword(s):

Early Stage ◽

Bottom Ash ◽

Relative Weight ◽

Main Reaction ◽

Reaction Products ◽

Coal Bottom Ash ◽

Heavy Metal Leaching ◽

Granulated Blast Furnace Slag ◽

Fine Aggregates ◽

Cementless Binder

This study investigated the use of coal bottom ash (bottom ash) and CaO-CaCl2-activated ground granulated blast furnace slag (GGBFS) binder in the manufacturing of artificial fine aggregates using cold-bonded pelletization. Mixture samples were prepared with varying added contents of bottom ash of varying added contents of bottom ash relative to the weight of the cementless binder (= GGBFS + quicklime (CaO) + calcium chloride (CaCl2)). In the system, the added bottom ash was not simply an inert filler but was dissolved at an early stage. As the ionic concentrations of Ca and Si increased due to dissolved bottom ash, calcium silicate hydrate (C-S-H) formed both earlier and at higher levels, which increased the strength of the earlier stages. However, the added bottom ash did not affect the total quantities of main reaction products, C-S-H and hydrocalumite, in later phases (e.g., 28 days), but simply accelerated the binder reaction until it had occurred for 14 days. After considering both the mechanical strength and the pelletizing formability of all the mixtures, the proportion with 40 relative weight of bottom ash was selected for the manufacturing of pilot samples of aggregates. The produced fine aggregates had a water absorption rate of 9.83% and demonstrated a much smaller amount of heavy metal leaching than the raw bottom ash.

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