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

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%.

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Preparation and characterisation of water soluble polyester coatings based on waste materials

Pigment & Resin Technology ◽

10.1108/prt-07-2016-0072 ◽

2017 ◽

Vol 46 (5) ◽

pp. 408-422 ◽

Cited By ~ 2

Author(s):

Soheir Youssef Tawfik ◽

Magdy Wadid Sabaa ◽

Ramzy Takawy Botros

Keyword(s):

Value Added ◽

Environmentally Friendly ◽

Water Soluble ◽

Raw Material ◽

Proton Nuclear Magnetic Resonance ◽

Resonance Spectroscopy ◽

Scanning Calorimetry ◽

Waste Products ◽

Pet Waste ◽

Content Type

Purpose The purpose of this paper is to prepare cheap and environmentally friendly water soluble polyester coatings through the glycolysis of poly(ethylene terephthalate) (PET) waste. Design/methodology/approach A secondary value-added polyester coatings were prepared from PET waste. The first step was the de-polymerisation of PET waste by 2,2-dimethyl-1,3-propanediol with different molar ratios in the presence of different concentrations of zinc acetate as trans-esterification catalyst. The de-polymerised product was characterised by Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1HNMR), differential scanning calorimetry and hydroxyl values. The polyesters were successfully synthesised by esterification of the glycolysed product with adipic acid, isophthalic acid, 2,2-dimethyl-1,3-propanediol and trimellitic anhydride in different ratios. FTIR and 1HNMR were used qualitatively and quantitatively to elucidate the structure of the prepared polyesters. Hydroxyl value and the physical properties of the prepared polyesters were also investigated. Two different curing agents were used to prepare the coatings based on the prepared polyesters. Findings Useful coating products were obtained by chemical (glycolysis) of post consumed PET wastes. The 2,2-dimethyl-1,3-propanediol was found to be good glycol in the glycolysis of PET. It was noticed that the rate of glycolysis increases with increasing the amount of catalyst, time of glycolysis and amount of 2,2-dimethyl-1,3-propanediol. N,N-Dimethylethanol amine was a good neutralising agent used for the preparation of water soluble coatings based on glycolysed product of PET. Practical implications The use of waste products like PET waste in water soluble coating systems will bring down the costs of the coatings and will also open a new market of recycled plastic materials and, hence, may provide a potential solution to the problems of solid waste management. It is an attractive option for environmentally friendly and efficient disposal of plastic waste. Originality/value The paper provides a potential way to use undesirable PET waste as industrial raw material. The coatings prepared are eco-friendly, soluble in water that can replace other expensive polyester coatings that are soluble in organic solvents and not environmentally coatings.

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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 ◽

10.3390/polym12061252 ◽

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.

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

High Performance Polymers ◽

10.1177/0954008317701823 ◽

2017 ◽

Vol 30 (4) ◽

pp. 475-479 ◽

Cited By ~ 5

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.

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

High Performance Polymers ◽

10.1177/0954008316671791 ◽

2016 ◽

Vol 29 (10) ◽

pp. 1139-1147 ◽

Cited By ~ 6

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%).

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

Polymers ◽

10.3390/polym13183177 ◽

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.

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

Polymers ◽

10.3390/polym12112433 ◽

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.

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Influence of e-Beam Irradiation on the Physicochemical Properties of Poly(polyol Succinate-co-Butylene Succinate) Ester Elastomers

Materials ◽

10.3390/ma13143196 ◽

2020 ◽

Vol 13 (14) ◽

pp. 3196

Author(s):

Marta Piątek-Hnat ◽

Kuba Bomba ◽

Jakub Pęksiński ◽

Agnieszka Kozłowska ◽

Jacek G. Sośnicki ◽

...

Keyword(s):

Succinic Acid ◽

Thermomechanical Analysis ◽

Resonance Spectroscopy ◽

Cross Link ◽

Scanning Calorimetry ◽

Water Contact ◽

Butylene Succinate ◽

Link Density ◽

Static Tensile ◽

Cross Link Density

The purpose of this research was synthesis and electron beam modification of novel ester elastomers consisting of sugar alcohol–succinic acid block and butylene glycol–succinic acid block. Four different alditols were used in the synthesis—sorbitol, erythritol, xylitol, and glycerol. The materials were irradiated with doses of 50, 100, and 150 kGy in order to determine which dose is the most beneficial. As expected, irradiation of the materials has led to the cross-link density becoming higher and improvement of the mechanical properties. Additionally, the materials were also sterilized in the process. The great advantage of elastomers described in the paper is the fact that they do not need chemical cross-linking agents or sensitizers in order to undergo radiation modification. The following tests were performed on cross-linked poly(polyol succinate-co-butylene succinate) elastomers: quasi-static tensile test, determination of cross-link density, differential scanning calorimetry (DSC), dynamic thermomechanical analysis (DMTA), wettability (water contact angle), and Fourier transform infrared spectroscopy (FTIR). In order to confirm successful synthesis, prepolymers were analyzed by nuclear magnetic resonance spectroscopy (1H NMR and 13C NMR).

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

High Performance Polymers ◽

10.1177/0954008320905362 ◽

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.

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A novel and highly efficient polymerization of sulfomethylated alkaline lignins via alkyl chain cross-linking method

Holzforschung ◽

10.1515/hf-2015-0043 ◽

2016 ◽

Vol 70 (4) ◽

pp. 297-304 ◽

Cited By ~ 9

Author(s):

Nanlong Hong ◽

Wei Yu ◽

Yuyuan Xue ◽

Weimei Zeng ◽

Jinhao Huang ◽

...

Keyword(s):

Group Analysis ◽

Gel Permeation Chromatography ◽

Water Soluble ◽

Raw Material ◽

Low Rank ◽

Proton Nuclear Magnetic Resonance ◽

Resonance Spectroscopy ◽

One Pot ◽

New Family ◽

High Degree

Abstract A new family of water-soluble lignosulfonate polymers with ultrahigh molecular weight (Mw) was developed based on alkali lignin (AL) as starting material in a one-pot reaction in two steps: sulfomethylation of AL as raw material led to AL-S and this material was subsequently cross-linked via alkylation with 1,6-dibromohexane (alkAL-S). Gel permeation chromatography showed a significant increase of Mw from 5200 Da of AL-S to 201 000 Da of alkAL-S with high degree of alkylation. Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance spectroscopy and functional group analysis confirmed the efficient polymerization by a nucleophilic substitution reaction mechanism. Additionally, alkAL-S with high Mw showed unexpected viscosity-reducing effect, stability and good rheological properties on a low-rank coal-water slurry (CWS), which are even better than those obtained by naphthalene sulfonate formaldehyde (NSF) as additive. The adsorption properties of the new products were also characterized via a quartz crystal microbalance combined with dissipation monitoring (QCM-D method). Cross-linked structure, large steric hindrance from high Mw and suitable amphiphilic properties of alkAL-S polymers contribute together to the highly improved dispersion performances for CWS.

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

High Temperature Materials and Processes ◽

10.1515/htmp-2015-0244 ◽

2017 ◽

Vol 36 (10) ◽

pp. 955-962 ◽

Cited By ~ 6

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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