Cd and Zn-incorporated polyesteramide coating materials from seed oil—A renewable resource

Cd and Zn metal (with completely filled ‘d’ orbital) incorporated linseed oil polyesteramides [Zn-LPEA and Cd-LPEA] were synthesized by in situ condensation polymerization reaction between linseed fattyamide diol (HELA), phthalic anhydride and divalent cadmium/zinc acetate (different mole ratios) obviating the use of any solvent. The structures of these resins were confirmed by FT-IR, ¹H NMR and ¹³C NMR spectral studies. The solubility of the resin was checked in different polar and non-polar solvents. The physico-chemical and physico-mechanical properties were studied by standard methods. Curing and thermal behavior were investigated by DSC and TGA techniques. The corrosion protective performance of coatings on mild steel strips was investigated by standard methods. Agar diffusion method was used to determine the antibacterial activities of these polymers. The studies revealed that the minor incorporation of divalent cadmium and zinc in virgin linseed oil based polyesteramide [LPEA] enhances the physico-mechanical and anticorrosive properties as well as reduces the curing temperature. Besides these properties they also show effective antibacterial behaviour against the Escherichia coli and Staphylococcus aureus. The Zn-LPEA and Cd-LPEA resins are, therefore, inexpensive coatings material, developed from renewable resource, for anti-corrosive and antibacterial applications.     

Studies on zinc-containing linseed oil based polyesteramide

For the first time the synthesis of zinc containing linseed oil based polyesteramide resins (Zn-LPEA-1 to Zn-LPERA-5) with different loadings of zinc acetate were carried out by in situ condensation polymerization reaction between linseed oil derived linseed fattyamide diol (HELA), phthalic anhydride and zinc acetate (divalent metal salt, different mole ratios) in the absence of any solvent. By-products such as water and acetic acid were removed by the application of vacuum technique. This approach was employed to overcome the use of volatile organic solvents [VOCs] during processing and application of the resin, that are ecologically harmful. The structure of the resin was confirmed by FT IR, ¹H NMR and ¹³C NMR spectral studies. Physico-chemical properties were studied by standard methods. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) was used to measure the thermal behaviour of the resin. The antibacterial studies of Zn-LPEA resins were carried out by agar diffusion method. Antibacterial activities of Zn-LPEA were compared with reported virgin linseed polyesteramide (LPEA) and zinc incorporated petroleum based polymers.     

Synthesis and characterization of poly(esteramide‐urethane) from linseed oil as anticorrosive coatings

Ethylene diamine polyesteramide (Ed‐PEA) was synthesized from N, N‐bis (2‐hydroxy ethyl) linseed oil fattyamide and ethylene diamine tetra acetic acid through condensation polymerization. It was further treated with toluylene 2,4‐diisocyanate (TDI) in different weight percentage to obtain urethane‐modified polyesteramide (Ed‐UPEA). The structural elucidation of Ed‐PEA and Ed‐UPEA were carried out by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopic techniques. Thermal studies of these resins were carried by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The coatings of urethane‐modified polyesteramide were prepared on mild steel strips and their anticorrosive behavior of in acid, alkali, water, and xylene were investigated. Thermal stability performance suggests that the system could be safely used upto 200°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Swelling kinetics of linseed oil‐based polymers

Kinetics of swelling and sorption behavior of copolymers (based on linseed oil, styrene, divinylbenzene, and acrylic acid via cationic and thermal polymerization) is studied in tetrahydrofuran (THF) at different temperatures. The values of n in the transport equation are found to be below 0.4, showing non‐Fickian or pseudo‐Fickian transport in the polymers. The dependence of diffusion coefficient on the composition and temperature has also been studied for the linseed oil‐based polymers. The diffusion coefficient in cationic samples decreases with an increase in the oil contents in the samples. In case of thermal samples, the diffusion coefficient first increases up to 30% oil contents and then decreases. The diffusion coefficient decreases with an increase in temperature for all of the linseed oil polymer samples. The sorption coefficient increases with an increase in the oil contents for all samples. The crosslink density (calculated from the THF swelling) ranges from 20.16 to 92.34 × 10⁶ mol/cm³ for cationic samples and 20.62 to 86.01 × 10⁶ mol/cm³ for thermal samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of water‐insoluble functional copolymers containing amide,amine, and carboxylic acid groups and their metal‐ion‐uptake properties

The crosslinked poly[N‐(3‐dimethylamino)propylmethacrylamide] [P(NDAPA)] and poly[N‐(3‐dimethylamino)propylmethacrylamide‐co‐acrylic acid] [P(NDAPA‐co‐AA)] were synthesized by radical polymerization. The resins were completely insoluble in water. The metal‐ion‐uptake properties were studied by a batch equilibrium procedure for the following metal ions: silver(I), copper(II), cadmium(II), zinc(II), lead(II), mercury(II), chromium(III), and aluminum(III). The P(NDAPA‐co‐AA) resin showed a lower metal‐ion affinity than P(NDAPA), except for Hg(II), which was retained at 71% at pH 2. At pH 5, the resin showed a higher affinity for Pb(II) (80%) and Cu(II) (60%), but its affinity was very low for Zn(II) and Cr(III). The polymer ligand–metal‐ion equilibrium was achieved during the first 20 min. By changing the pH, we found it possible to remove between 60 and 70% of Cd(II) and Zn(II) ions with (1M, 4M) HClO₄ and (1M, 4M) HNO₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5232–5239, 2006     

Synthesis,characterization and polychelatogenic properties of poly[(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid)‐co‐(methacrylic acid)]

Poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid), poly(methacrylic acid), and five copolymers of poly[(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)‐co‐(methacrylic acid)] were synthesized by radical polymerization and obtained in yields >97%. The polymers were characterized by FT‐IR, [¹H]NMR, and [¹³C]NMR and studied by means of the Liquid‐phase Polymer‐based Retention (LPR) technique. The metal ion retention ability of the copolymers for Cu(II), Cd(II), Co(II), Hg(II), Ni(II), Zn(II), Cr(III) and Ag(I) was investigated at different pH values because of their environmental and analytical interest. The retention profiles of the copolymers were compared with those of the corresponding homopolymers and retention of metal ions was found to increase with increasing pH. © 2001 Society of Chemical Industry     

Cashew nut shell liquid based t‐BOC protected alternating “high ortho” copolymer as a possible e‐beam resist: Characterization using multi‐dimensional NMR spectroscopy

A cardanol/m‐cresol‐based copolymer was esterified using di‐tert‐butyl dicarbonate (t‐BOC), which makes it a suitable candidate as a possible e‐beam resists. This work reports a full characterization of the product using the techniques of FTIR and UV–Visible spectroscopy, one dimensional ¹H NMR, ¹³C NMR, DEPT‐135. Two dimensional NMR experiments such as, COSY, HSQC, and HMBC have been employed for exhaustive probing of the microstructural details of this derivatized copolymer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

13C‐NMR study on cure‐accelerated phenol–formaldehyde resins with carbonates

Both liquid‐ and solid‐state ¹³C‐NMR spectroscopies were employed to investigate the cure‐acceleration effects of three carbonates [propylene carbonate (PC), sodium carbonate (NC), and potassium carbonate (KC)] on liquid and cured phenol–formaldehyde (PF) resins. The liquid‐phase ¹³C‐NMR spectra showed that the cure‐acceleration mechanism in the PC‐added PF resin seemed to be involved in increasing reactivity of the phenol rings, while the addition of both NC and KC into PF resin apparently resulted in the presence of ortho–ortho methylene linkages. Proton spin‐lattice rotating frame relaxation time (T_1ρH) measured by solid‐state ¹³C‐CP/MAS‐NMR spectroscopy was smaller for the cure‐accelerated PF resins than for that of the control PF resin. The result indicated that cure‐accelerated PF resins are less rigid than the control PF resin. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 841–851, 2000     

Studies on urethane‐modified alumina‐filled polyesteramide anticorrosive coatings cured at ambient temperature

Coatings prepared from polyesteramide resin synthesized from linseed oil, a renewable resource, have been found to show improved physicomechanical and anticorrosive characteristics. These properties are further improved when aluminum is incorporated in the polyesteramide resin. The coatings of this resin are generally obtained by baking at elevated temperatures. With a view toward the use of linseed oil, as a precursor for the synthesis of polyesteramide resins and to cure their coatings at ambient temperature, toluylene diisocyanate (TDI) was incorporated into polyesteramide and alumina‐filled polyesteramide in varying proportions to obtain urethane‐modified resins. The latter resins were found to cure at room temperature. The broad structural features of the urethane‐modified polyesteramide and alumina‐filled polyesteramide were confirmed by FTIR and ¹H–NMR spectroscopies. Scratch hardness; impact resistance; bending resistance; specular gloss; and resistance to acid, alkali, and organic solvents of the coatings of these resins were determined by standard methods. Physicomechanical and anticorrosive properties, specular gloss, and thermal stability of the urethane‐modified alumina‐filled polyesteramide coatings were found to be at higher levels among these resins. It was found that TDI could be incorporated in polyesteramide up to only 6 wt %, such that above this loading its properties started to deteriorate, whereas alumina‐filled polyesteramide could take up to 10 wt % TDI. Explanation is provided for the increase in scratch hardness and impact resistance above 6 and 10 wt % addition of TDI in polyesteramide and alumina‐filled polyesteramide, respectively, as well as for the decrease in flexibility and resistance to solvents, acid, and alkali of coatings of these resins above these limits of TDI addition. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1855–1865, 2001     

Development of linseed oil based polyesteramide without organic solvent at lower temperature

Linseed oil based polyesteramide was synthesized at lower temperature in the absence of organic solvent through condensation polymerization reaction [Sf‐LPEA]. In this reaction N,N‐bis(2‐hydroxyethyl) linseed oil fatty amide and phthalic anhydride were heated at temperature lower than their onset of melting points and the by‐product, such as water was removed by application of vacuum technique. This approach was employed to overcome the use of volatile organic solvents used during processing and application of resin, which are ecologically harmful. The solubility of Sf‐LPEA was checked in different polar and nonpolar solvents. The FTIR, ¹H NMR, and ¹³C NMR spectral techniques were used to confirm the structure of Sf‐LPEA. The physicochemical, physicomechanical, and chemical resistance properties of the resin were investigated by standard methods. DSC and TGA were used to determine, respectively, the curing behavior and thermal stability of the resin. The comparative study of these properties of Sf‐LPEA with reported polyesteramide [LPEA], which are normally synthesized at higher temperature in organic solvent, was done. It was found that Sf‐LPEA exhibited improved physicomechanical, chemical resistance properties, and higher thermal stability compared with LPEA, and hence can find application as corrosion protective coating. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1143–1148, 2007     

Water‐soluble copolymers of 1‐vinyl‐2‐pyrrolidone and acrylamide derivatives: synthesis,characterization, and metal binding capability studied by liquid‐phase polymer‐based retention technique

Radical copolymerizations of 1‐vinyl‐2‐pyrrolidone with acrylamide and N,N′‐dimethylacrylamide at different feed ratios were investigated. The copolymers were characterized by Fourier transform infrared spectroscopy, ¹H NMR, and ¹³C NMR spectroscopy. The copolymer composition was determined from the ¹H NMR spectra and found to be statistical. The metal complexation of poly(acrylamide‐co‐1‐vinyl‐2‐pyrrolidone) and poly(N,N′‐dimethylacrylamide‐co‐1‐vinyl‐2‐pyrrolidone) for the metal ions Cu(II), Co(II), Ni(II), Cd(II), Zn(II), Pb(II), Fe(III), and Cr(III) were investigated in an aqueous phase. The liquid‐phase polymer‐based retention method is based on the retention of inorganic ions by soluble polymers in a membrane filtration cell and subsequent separation of low‐molecular compounds from the polymer complex formed. The metal ion interaction with the hydrophilic polymers was determined as a function of the pH and the filtration factor. Poly(N,N‐dimethylacrylamide‐co‐1‐vinyl‐2‐pyrrolidone) showed a higher affinity for the metal ions than poly(acrylamide‐co‐1‐vinyl‐2‐pyrrolidone). According to the interaction pattern obtained, Cr(III) and Cu(II) formed the most stable complexes at pH 7. Pb(II) and Zn(II) were not retained. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 741–750, 1999     

Highly efficient and reversible CO2 capture by tunable anion‐functionalized macro‐porous resins

Anion functionalized strategy has been proposed for the synthesis of macro‐porous resins [IRA‐900][An] through the neutral reaction of the basic resin [IRA‐900][OH] with the corresponding donors. Combining CO₂ adsorption results and FT‐IR, solid‐state ¹³C NMR characterization as well as quantum chemical calculations, chemical adsorption mechanism was verified and tunable capture of CO₂ was realized. Among them, the anion functionalized resin [IRA‐900][Triz] exhibits an extremely high adsorption capacity (4.02 mmol g^?1 at 25°C, 0.15 bar), outperforming many other good adsorbents. Finally, we discuss the thermostability and recycling stability of [IRA‐900][Triz], which shows a great potential in the industrial capture of CO₂. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3008–3015, 2017     

13C‐NMR study on cure‐accelerated phenol‐formaldehyde resins with carbonates

Both liquid‐ and solid‐state carbon‐13–nuclear magnetic resonance (¹³C‐NMR) spectroscopies were used to investigate the cure acceleration effects of three carbonates (propylene carbonate, sodium carbonate, and potassium carbonate) on liquid and cured phenol‐formaldehyde (PF) resins. The liquid‐phase ¹³C‐NMR spectra showed that the cure acceleration mechanism in the propylene carbonate‐added PF resin seemed to be involved in increasing reactivity of the phenol rings, whereas the addition of both sodium carbonate and potassium carbonate into PF resin apparently resulted in the presence of ortho–ortho methylene linkages. Proton spin‐lattice rotating frame relaxation time (T_1ρH) measured by solid‐state ¹³C cross polarization/magic‐angle spinning NMR spectroscopy was smaller for the cure‐accelerated PF resins than that of the control PF resin. The result indicated that the cure‐accelerated PF resins are less rigid than the control PF resin. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1284–1293, 2000     

Nonionic water‐soluble polymer: Preparation,characterization, and application of poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) as a polychelatogen

The free‐radical copolymerization of water‐soluble poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) was carried out with a feed monomer ratio of 75:25 mol %, and the total monomer concentration was 2.67M. The synthesis of the copolymer was carried out in dioxane at 70°C with benzoyl peroxide as the initiator. The copolymer composition was obtained with elemental analysis and ¹H‐NMR spectroscopy. The water‐soluble polymer was characterized with elemental analysis, Fourier transform infrared, ¹H‐ and ¹³C‐NMR spectroscopy, and thermal analysis. Additionally, viscosimetric measurements of the copolymer were performed. The thermal behavior of the copolymer and its complexes were investigated with differential scanning calorimetry (DSC) and thermogravimetry techniques under a nitrogen atmosphere. The copolymer showed high thermal stability and a glass transition in the DSC curves. The separation of various metal ions by the water‐soluble poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) reagent in the aqueous phase with liquid‐phase polymer‐based retention was investigated. The method was based on the retention of inorganic ions by this polymer in a membrane filtration cell and subsequent separation of low‐molar‐mass species from the polymer/metal‐ion complex formed. Poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) could bind metal ions such as Cr(III), Co(II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) in aqueous solutions at pHs 3, 5, and 7. The retention percentage for all the metal ions in the polymer was increased at pH 7, at which the maximum retention capacity could be observed. The interaction of inorganic ions with the hydrophilic polymer was determined as a function of the pH and filtration factor. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 178–185, 2006     

Studies on a newly developed linseed oil‐based alumina‐filled polyesteramide anticorrosive coating

Polyesteramide (PEA) and alumina‐filled polyesteramide (APEA) resins were synthesized from N,N′‐bis(2 hydroxyethyl) linseed amide. The FTIR, ¹H‐NMR, DSC, TGA, thermal curing, and physico‐chemical characterization of these polymers were carried out. The coatings of PEA and APEA were made on mild steel strips. The mechanical behavior and protective efficiency of these coatings in acid, alkali, and organic solvents were investigated. APEA coatings have been found to show superior performance in comparison to other coatings. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1679–1687, 1999     

Characterization of morphology in chemically modified styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene by solid‐state nuclear magnetic resonance

Multiphase triblock styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene (SEBS) copolymers chemically modified with maleic anhydride (MAH) in the presence of a radical initiator by reactive extrusion were studied by solid‐state ¹H‐NMR and ¹³C‐NMR. In the experiments performed, the concentrations of MAH and initiator were kept constant, whereas the temperature profile in the extruder was varied. Samples with known extents of grafting and crosslinking were analyzed with NMR with techniques based on proton spin diffusion to investigate the microphase structure of the modified copolymers. The ¹³C‐NMR results show that the size of the rigid domains was about 15 nm and was not significantly changed by the modification. Alterations in the rubbery phase were illustrated by measured changes in proton spin‐spin (T₂) relaxation times. The fraction of protons having intermediate mobilities increased slightly in modified SEBS with respect to that observed in unmodified copolymers. These results were found to be independent of the extruder temperature profiles used, at least in the range studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Removal of lead,cadmium and zinc from aqueous solutions by precipitation with sodium Di‐(n‐octyl) phosphinate

Sodium di‐(n‐octyl) phosphinate (NaL) was used as a precipitating agent to remove heavy metals from aqueous nitrate solutions. Cadmium, zinc and mixtures of lead, cadmium and zinc were precipitated in the form of PbL_2(s), CdL_2(s), and ZnL_2(s). Lowering the pH of the feed solution reduced the removal of the metals as some of the phosphinate precipitated in the acid form as HL_(S). The removal of lead, cadmium, and zinc, from a solution containing the three metals gave a selectivity in the order Zn > Pb > Cd. Predictions of an equilibrium‐constant model, using measured solubility products of the precipitates and literature values of stability constants, gave metal removals, loss of precipitating agent, and equilibrium pH in good agreement with measured values.     

Linseed Oil‐Based Thermosets by Aza‐Michael Polymerization

Aza‐Michael addition on acrylated linseed oil (AELO) is performed to synthetize biobased bulk thermosets without any catalyst. First, acrylation of epoxidized linseed oil (ELO) allows to obtain acrylate functions with vicinal hydroxyl groups which enhance the reactivity of acrylates. The autocatalytic effect of hydroxyl groups on acrylate monomers is highlighted by kinetic studies monitored by NMR and FTIR analyses on model molecules. Then, Priamine 1071, amine terminated poly(propyleneoxide) (PPO) and meta‐xylylenediamine (MXDA) are used as cross‐linkers with AELO. Curing kinetics are studied by DSC analyses to compare the reactivity of these structures. Priamine 1071 shows the highest reactivity; curing at room temperature is performed and high conversion is reached. Two enthalpies are observed with MXDA and only one at high temperature for PPO‐based materials. Thermosets with a large range of mechanical properties are finally obtained from soft materials with PPO‐diamine to hard materials with MXDA. Practical Applications: Thermosets are obtained by curing AELO with various diamines via aza‐Michael reaction. Model reaction allows to demonstrate catalytic effect of hydroxyl groups on Aza‐Michael reaction of acrylated oil with amines. Hence, linseed oil is a promising resource in terms of sustainable development in polymer science.     

Ambient‐cured polyesteramide‐based anticorrosive coatings from linseed oil—A sustainable resource

Ambient‐cured polyesteramide (APEA) coating resin synthesized from dihydroxy fatty amide obtained from linseed oil, a sustainable resource, and poly(styrene‐co‐maleic anhydride), a bifunctional acid component, was found to exhibit improved physicomechanical and anticorrosive properties. The structural elucidation of APEA resin has been carried out by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopies. The physicomechanical and chemical resistance properties were investigated by standard methods. The corrosion resistance performance was evaluated in acid, alkali, and organic solvent. The thermal behavior was studied by TGA technique. A comparative study of these properties of APEA with reported baked polyesteramide (PEA) coatings was carried out. A remarkable improvement in the drying property of APEA was observed. The APEA coatings also showed improved physicomechanical and anticorrosive properties as compared to the baked PEA coatings. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1818–1824, 2005     

Soybean and linseed oil‐based composites reinforced with wood flour and wood fibers

Composites consisting of a conjugated linseed or soybean oil‐based thermoset reinforced with wood flour and wood fibers have been prepared by free radical polymerization. The thermoset resin consists of a copolymer of conjugated linseed oil (CLO) or conjugated soybean oil (CSO), n‐butyl methacrylate (BMA), divinylbenzene (DVB), and maleic anhydride (MA). The composites were cured at 180°C and 600 psi and postcured for 2 h at 200°C under atmospheric pressure. The effect of varying filler load, time of cure, filler particle size, origin of the fillers, and resin composition has been assessed by means of tensile tests, DMA, TGA, Soxhlet extraction followed by ¹H‐NMR spectroscopic analysis of the extracts, and DSC. The best processing conditions have been established for the pine wood flour composites. It has been observed that the addition of MA to the resin composition improves the filler‐resin interaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012