scholarly journals Structural and Thermal Properties of Ethylene-Norbornene Copolymers Obtained Using Vanadium Homogeneous and SIL Catalysts

Polymers ◽  
2020 ◽  
Vol 12 (11) ◽  
pp. 2433
Author(s):  
Paweł Groch ◽  
Anna Bihun-Kisiel ◽  
Aleksandra Piontek ◽  
Wioletta Ochędzan-Siodłak
Keyword(s):  
Thermal Properties ◽  
Reactivity Ratio ◽  
Proton Nuclear Magnetic Resonance ◽  
Sequence Length ◽  
Resonance Spectroscopy ◽  
Scanning Calorimetry ◽  
Reaction Conditions ◽  
Copolymer Microstructure ◽  
Chain Termination Reaction ◽  
Catalyst Systems

The series of ethylene-norbornene (E-NB) copolymers was obtained using different vanadium homogeneous and supported ionic liquid (SIL) catalyst systems. The 13C and 1H NMR (carbon and proton nuclear magnetic resonance spectroscopy) together with differential scanning calorimetry (DSC) were applied to determine the composition of copolymers such as comonomer incorporation (CNB), monomer dispersity (MD), monomer reactivity ratio (re), sequence length of ethylene (le) and tetrad microblock distributions. The relation between the type of catalyst, reaction conditions and on the other hand, the copolymer microstructure, chain termination reaction analyzed by the type of unsaturation are discussed. In addition, the thermal properties of E-NB copolymers such as the melting and crystallization behavior, like also the heterogeneity of composition described by successive the self-nucleation and annealing (SSA) and the dispersity index (DI) were determined.

Thermal properties of a series of tetrafunctional fluorene-based oxazines/P-a blends

2016 ◽  
Vol 29 (10) ◽  
pp. 1139-1147 ◽  
Author(s):  
Zi Sang ◽  
Tiantian Feng ◽  
Wenbin Liu ◽  
Jun Wang ◽  
Mehdi Derradji
Keyword(s):  
Thermal Stability ◽  
Differential Scanning Calorimetry ◽  
Thermal Properties ◽  
Mechanical Analysis ◽  
Proton Nuclear Magnetic Resonance ◽  
Primary Amines ◽  
Resonance Spectroscopy ◽  
High Glass Transition Temperature ◽  
Scanning Calorimetry ◽  
Good Thermal Stability

A new series of aniline and aniline-mixed tetrafunctional fluorene-based oxazine monomers were synthesized using 2,7-hydroxy-9,9-bis-(4-hydroxyphenyl) fluorene, paraformaldehyde, and primary amines (including aniline or aniline mixed with n-butylamine or n-octylamine composition). Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy were used to characterize the structure of the monomers. The copolymers were obtained by adding the monomers into a typical monofunctional polybenzoxazine (phenol-aniline-based benzoxazine). Differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis were performed to study the thermal properties of the copolymers. The copolymers exhibited high glass transition temperature values (164–201°C). A good thermal stability was also obtained with a 5% weight loss temperature over 355°C and high char yields at 800°C (42–50%).

Natural rubber grafted poly(methyl methacrylate) as compatibilizer in 50/50 natural rubber/nitrile rubber blend

2016 ◽  
Vol 49 (5) ◽  
pp. 422-439 ◽  
Author(s):  
Supat Moolsin ◽  
Nattawud Saksayamkul ◽  
Adul Na Wichien
Keyword(s):  
Thermal Properties ◽  
Natural Rubber ◽  
Methyl Methacrylate ◽  
Graft Copolymers ◽  
Nitrile Rubber ◽  
Proton Nuclear Magnetic Resonance ◽  
Tensile Fracture ◽  
Resonance Spectroscopy ◽  
Scanning Calorimetry ◽  
Oil Resistance

The effects of graft copolymers applied as compatibilizers for natural rubber/nitrile rubber (NR/NBR) blends at 50/50 (w/w) on cure characteristics, mechanical properties, thermal properties, oil resistance, and morphology were investigated. The graft copolymers of methyl methacrylate (MMA) onto NR initiated by benzoyl peroxide (NR- g-PMMA<BPO>) and by potassium persulfate (NR- g-PMMA<PPS>) under emulsion polymerization were synthesized and used to compatibilize the blends. The structures of the copolymers were characterized by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy. NR was blended with NBR via a two-roll mill at 70°C under the compatibilizer loading ranging from 0 to 10 parts per hundred of rubber (phr). The results showed that the tensile property and tear strength of the blends increased with the increasing amount of NR- g-PMMA<BPO> as a compatibilizer. Thermal aging determined in terms of tensile properties exhibited the smaller difference between before and after aging in an oven with the increasing compatibilizer loading. The morphology of the compatibilized NR/NBR vulcanizates was investigated by scanning electron microscopy of the tensile fracture surfaces, which exhibited the improvement of interfacial adhesion between the two rubber phases. The thermal properties of compatibilized NR/NBR vulcanizates were reported in terms of a glass transition temperature under differential scanning calorimetry and dynamic mechanical analysis. The incorporation of an appropriate amount of the compatibilizer into the blends apparently improved the oil resistance of NR. Among them, the blend filled with 7.5 phr of NR- g-PMMA<BPO> showed the lowest volume change in IRM 903 oil.

scholarly journals Statistical Copolymers of N-Vinylpyrrolidone and Isobornyl Methacrylate via Free Radical and RAFT Polymerization: Monomer Reactivity Ratios, Thermal Properties, and Kinetics of Thermal Decomposition

Polymers ◽  
2021 ◽  
Vol 13 (5) ◽  
pp. 778
Author(s):  
Olga Kokkorogianni ◽  
Philippos Kontoes-Georgoudakis ◽  
Maria Athanasopoulou ◽  
Nikolaos Polizos ◽  
Marinos Pitsikalis
Keyword(s):  
Thermal Properties ◽  
Free Radical ◽  
Raft Polymerization ◽  
Structural Parameters ◽  
Reactivity Ratio ◽  
Sequence Length ◽  
Reactivity Ratios ◽  
Scanning Calorimetry ◽  
Reversible Addition ◽  
Kinetics Of

The synthesis of statistical copolymers of N-vinylpyrrolidone (NVP) with isobornyl methacrylate (IBMA) was conducted by free radical and reversible addition-fragmentation chain transfer (RAFT) polymerization. The reactivity ratios were estimated using the Finemann-Ross, inverted Fineman-Ross, Kelen-Tüdos, extended Kelen-Tüdos and Barson-Fenn graphical methods, along with the computer program COPOINT, modified to both the terminal and the penultimate models. According to COPOINT the reactivity ratios were found to be equal to 0.292 for NVP and 2.673 for IBMA for conventional radical polymerization, whereas for RAFT polymerization and for the penultimate model the following reactivity ratios were obtained: r11 = 4.466, r22 = 0, r21 = 14.830, and r12 = 0 (1 stands for NVP and 2 for IBMA). In all cases, the NVP reactivity ratio was significantly lower than that of IBMA. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length. The thermal properties of the copolymers were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and differential thermogravimetry (DTG). The results were compared with those of the respective homopolymers.

scholarly journals Analysis of Bio-Based Fatty Esters PCM’s Thermal Properties and Investigation of Trends in Relation to Chemical Structures

2019 ◽  
Vol 9 (2) ◽  
pp. 225 ◽  
Author(s):  
Rebecca Ravotti ◽  
Oliver Fellmann ◽  
Nicolas Lardon ◽  
Ludger Fischer ◽  
Anastasia Stamatiou ◽  
...  
Keyword(s):  
Thermal Properties ◽  
Phase Change ◽  
Energy Demand ◽  
Phase Change Materials ◽  
Arachidic Acid ◽  
Resonance Spectroscopy ◽  
Scanning Calorimetry ◽  
Fatty Esters ◽  
Latent Heat Storage ◽  
Chemical Structures

As global energy demand increases while primary sources and fossil fuels’ availability decrease, research has shifted its focus to thermal energy storage systems as alternative technologies able to cover for the mismatch between demand and supply. Among the different phase change materials available, esters possess particularly favorable properties with reported high enthalpies of fusion, low corrosivity, low toxicity, low supercooling, thermal and chemical stability as well as biodegradability and being derived from renewable feedstock. Despite such advantages, little to no data on the thermal behavior of esters is available due to low commercial availability. This study constitutes a continuation of previous works from the authors on the investigation of fatty esters as novel phase change materials. Here, methyl, pentyl and decyl esters of arachidic acid, and pentyl esters of myristic, palmitic, stearic and behenic acid are synthesized through Fischer esterification with high purities and their properties are studied. The chemical structures and purities are confirmed through Attenuated Total Reflectance Infrared Spectroscopy, Gas Chromatography coupled with Mass Spectroscopy and Nuclear Magnetic Resonance Spectroscopy, while the determination of the thermal properties is performed through Differential Scanning Calorimetry and Thermogravimetric Analysis. In conclusion, some correlations between the melting temperatures and the chemical structures are discovered, and the fatty esters are assessed based on their suitability as phase change materials for latent heat storage applications.

scholarly journals Synthesis and Self-Assembly of Poly(N-Vinylcaprolactam)-b-Poly(ε-Caprolactone) Block Copolymers via the Combination of RAFT/MADIX and Ring-Opening Polymerizations

Polymers ◽  
2020 ◽  
Vol 12 (6) ◽  
pp. 1252
Author(s):  
Rodolfo M. Moraes ◽  
Layde T. Carvalho ◽  
Gizelda M. Alves ◽  
Simone F. Medeiros ◽  
Elodie Bourgeat-Lami ◽  
...  
Keyword(s):  
Block Copolymers ◽  
Ring Opening ◽  
Chain Transfer ◽  
Fluorescence Probe ◽  
Size Exclusion ◽  
Proton Nuclear Magnetic Resonance ◽  
Solution Temperature ◽  
Copolymer Composition ◽  
Resonance Spectroscopy ◽  
Scanning Calorimetry

Well-defined amphiphilic, biocompatible and partially biodegradable, thermo-responsive poly(N-vinylcaprolactam)-b-poly(ε-caprolactone) (PNVCL-b-PCL) block copolymers were synthesized by combining reversible addition-fragmentation chain transfer (RAFT) and ring-opening polymerizations (ROP). Poly(N-vinylcaprolactam) containing xanthate and hydroxyl end groups (X–PNVCL–OH) was first synthesized by RAFT/macromolecular design by the interchange of xanthates (RAFT/MADIX) polymerization of NVCL mediated by a chain transfer agent containing a hydroxyl function. The xanthate-end group was then removed from PNVCL by a radical-induced process. Finally, the hydroxyl end-capped PNVCL homopolymer was used as a macroinitiator in the ROP of ε-caprolactone (ε-CL) to obtain PNVCL-b-PCL block copolymers. These (co)polymers were characterized by Size Exclusion Chromatography (SEC), Fourier-Transform Infrared spectroscopy (FTIR), Proton Nuclear Magnetic Resonance spectroscopy (1H NMR), UV–vis and Differential Scanning Calorimetry (DSC) measurements. The critical micelle concentration (CMC) of the block copolymers in aqueous solution measured by the fluorescence probe technique decreased with increasing the length of the hydrophobic block. However, dynamic light scattering (DLS) demonstrated that the size of the micelles increased with increasing the proportion of hydrophobic segments. The morphology observed by cryo-TEM demonstrated that the micelles have a pointed-oval-shape. UV–vis and DLS analyses showed that these block copolymers have a temperature-responsive behavior with a lower critical solution temperature (LCST) that could be tuned by varying the block copolymer composition.

Heat-resistant and photoluminescent indole-based poly(ether sulfone)s

2017 ◽  
Vol 30 (4) ◽  
pp. 475-479 ◽  
Author(s):  
Wenxuan Wei ◽  
Li Yang ◽  
Guanjun Chang
Keyword(s):  
Thermal Stability ◽  
High Performance ◽  
Proton Nuclear Magnetic Resonance ◽  
Resonance Spectroscopy ◽  
Condensation Polymerization ◽  
High Glass Transition Temperature ◽  
Scanning Calorimetry ◽  
Good Thermal Stability ◽  
High Performance Polymers ◽  
Good Agreement

Indole-based poly(ether sulfone)s (PINESs), as novel high-performance polymers, have been obtained by the condensation polymerization of 4-hydroxyindole and hydroquinone with activated difluoro monomers via a catalyst-free nucleophilic substitution reaction. The structures of the polymers are characterized by means of Fourier transform infrared and proton nuclear magnetic resonance spectroscopy, and the results show good agreement with the proposed structures. Differential scanning calorimetry and thermogravimetric analysis measurements exhibit that polymers possess high glass transition temperature ( Tgs > 245°C) and good thermal stability with high decomposition temperatures ( Tds > 440°C). In addition, due to their special structure, PINESs are endowed with significantly strong photonic luminescence in N, N-dimethylformamide.

scholarly journals Synthesis of Hydrophilic Poly(butylene succinate-butylene dilinoleate) (PBS-DLS) Copolymers Containing Poly(ethylene glycol) (PEG) of Variable Molecular Weights

Polymers ◽  
2021 ◽  
Vol 13 (18) ◽  
pp. 3177
Author(s):  
Moein Zarei ◽  
Miroslawa El Fray
Keyword(s):  
Molecular Weight ◽  
Thermal Properties ◽  
Ethylene Glycol ◽  
Polymeric Materials ◽  
Glycol Succinate ◽  
Resonance Spectroscopy ◽  
Scanning Calorimetry ◽  
Water Contact ◽  
Butylene Succinate ◽  
Molecular Weights

Polymeric materials have numerous applications from the industrial to medical fields because of their vast controllable properties. In this study, we aimed to synthesize series of poly(butylene succinate-dilinoleic succinate-ethylene glycol succinate) (PBS-DLS-PEG) copolymers, by two-step polycondensation using a heterogeneous catalyst and a two-step process. PEG of different molecular weights, namely, 1000 g/mol and 6000 g/mol, was used in order to study its effect on the surface and thermal properties. The amount of the PBS hard segment in all copolymers was fixed at 70 wt%, while different ratios between the soft segments (DLS and PEG) were applied. The chemical structure of PBS-DLS-PEG was evaluated using Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. Gel permeation chromatography was used to determine the molecular weight and dispersity index. The results of structural analysis indicate the incorporation of PEG in the macrochain. The physical and thermal properties of the newly synthesized copolymers were also evaluated using water contact angle measurements, differential scanning calorimetry and dynamic thermomechanical analysis. It was found that increasing the amount of PEG of a higher molecular weight increased the surface wettability of the new materials while maintaining their thermal properties. Importantly, the two-step melt polycondensation allowed a direct fabrication of a polymeric filament with a well-controlled diameter directly from the reactor. The obtained results clearly show that the use of two-step polycondensation in the melt allows obtaining novel PBS-DLS-PEG copolymers and creates new opportunities for the controlled processing of these hydrophilic and thermally stable copolymers for 3D printing technology, which is increasingly used in medical techniques.

Preparation and properties of silane-modified cardanol–benzoxazine for hydrophobic coating

2020 ◽  
pp. 009524432093398
Author(s):  
Wenzheng Zhang ◽  
Ning Jiang ◽  
Tingting Zhang ◽  
Tinghao Zhang
Keyword(s):  
Char Yield ◽  
Raw Material ◽  
Advanced Technology ◽  
Proton Nuclear Magnetic Resonance ◽  
Polymerization Reaction ◽  
Resonance Spectroscopy ◽  
Scanning Calorimetry ◽  
Water Contact ◽  
Coating Application ◽  
Cashew Nut

Cardanol is a kind of green industrial raw material, refined from cashew nut shell oil by advanced technology, which has shown potential for anticorrosion coating application. A new cardanol-based benzoxazine monomer (CB) was synthesized by Mannich condensation of a cardanol, paraformaldehyde, and cardanol aldehyde amine (Carala), which was prepared based on cardanol, paraformaldehyde, and triethylenetetramine, and finally, the cardanol-based benzoxazines containing amino group were modified by silane (CBSi). Cardanol, Carala, and CB were characterized by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy. Furthermore, the cured films have been evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. The result of DSC of CB and CBSi showed that curing behavior of CBSi was similar to that of CB; however, the enthalpy of polymerization reaction corresponding to CB and CBSi is 84.7 J g−1 and 91.3 J g−1, respectively, and exothermic enthalpy of CBSi is slightly higher than that of CB. TGA results illuminated that the thermal stability and char yield of cardanol-based polybenzoxazine could be enhanced due to increment of silane, and residual char yield at 700°C of CBSi30 is 13%. Especially, incorporation of silane could improve the water contact angle, which can increase from 78.7° to 98.9° when the ratio of γ-(2,3-epoxypropoxy) propytrimethoxysilane to CB increases from 0% to 30%.

Synthesis and thermal properties of phenol- and amine-capped main-chain benzoxazine oligomers with multiple methyl substitutions

2020 ◽  
Vol 32 (7) ◽  
pp. 823-834
Author(s):  
Lei Zhang ◽  
Jiale Mao ◽  
Shuang Wang ◽  
Yiting Zheng
Keyword(s):  
Thermal Stability ◽  
Thermal Properties ◽  
Main Chain ◽  
Chemical Shifts ◽  
Char Yield ◽  
Curing Temperature ◽  
Proton Nuclear Magnetic Resonance ◽  
Resonance Spectroscopy ◽  
Chemical Structures ◽  
End Capping

A series of main-chain benzoxazine oligomers with different methyl substitutions are successfully synthesized. Chemical structures are analyzed by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and gel permeation chromatography. Effects of methyl substitutions on chemical shifts of protons in oxazine ring and thermal properties, including glass transition temperature, thermal stability, and char yield, are discussed. The influences of methyl substitutions on different positions are demonstrated: (i) substitution on phenols induces obvious increase in curing temperature while substitution on amine does not show apparent impact; (ii) substitution at different positions results in T g variation, following the sequence of none-substitution > substitution at end-capping > substitution on diamines in main-chain > substitution on bisphenols in main-chain; and (iii) substitution at end-capping would cause apparent deterioration in thermal stability while substitution on diamines in main-chain would benefit thermal stability and char yield. Experimental results and related explanations are provided in detail.

Synthesis and Characterization of Poly (styrene-co-butyl acrylate)/Silica Aerogel Nanocomposites by in situ AGET ATRP: Investigating Thermal Properties

2017 ◽  
Vol 36 (10) ◽  
pp. 955-962 ◽  
Author(s):  
Khezrollah Khezri ◽  
Yousef Fazli
Keyword(s):  
Molecular Weight ◽  
Butyl Acrylate ◽  
Silica Aerogel ◽  
Size Exclusion ◽  
Proton Nuclear Magnetic Resonance ◽  
Molar Ratio ◽  
Resonance Spectroscopy ◽  
Gravimetric Analysis ◽  
Scanning Calorimetry ◽  
Exclusion Chromatography

AbstractHydrophilic silica aerogel nanoparticles surface was modified with hexamethyldisilazane. Then, the resultant modified nanoparticles were used in random copolymerization of styrene and butyl acrylate via activators generated by electron transfer for atom transfer radical polymerization. Conversion and molecular weight determinations were performed using gas and size exclusion chromatography respectively. Addition of modified nanoparticles by 3 wt% results in a decrease of conversion from 68 to 46 %. Molecular weight of copolymer chains decreases from 12,500 to 7,500 g.mol–1 by addition of 3 wt% modified nanoparticles; however, PDI values increase from 1.1 to 1.4. Proton nuclear magnetic resonance spectroscopy results indicate that the molar ratio of each monomer in the copolymer chains is approximately similar to the initial selected mole ratio of them. Increasing thermal stability of the nanocomposites is demonstrated by thermal gravimetric analysis. Differential scanning calorimetry also shows a decrease in glass transition temperature by increasing modified silica aerogel nanoparticles.

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