In situ development of Zn/Cd‐incorporated poly(esteramide‐urethane) from sustainable resource

It was for the first time we attempted to develop zinc and cadmium incorporated linseed oil based poly(esteramide‐urethane) [Zn/Cd‐LPEAUr], and investigated their structure, mechanism, and properties. The resin was synthesized in situ by the reaction of linseed oil derived fatty amide diol [HELA], divalent zinc/cadmium acetate and toluylene‐2, 4 (6), diisocyanate [TDI; 2–12 wt %] with minimal solvent. The structural elucidation of Zn/Cd‐LPEAUr was carried out by FTIR, ¹H‐NMR, and ¹³C‐NMR spectral techniques. TGA and DSC techniques were used to measure the thermal stability and curing behavior of these resins, respectively. The physicomechanical and chemical/corrosion resistance properties were investigated by standard laboratory methods. The performance of Zn/Cd‐LPEAUr coating was compared with reported oil based polyesteramide. Antibacterial test of the resins were performed by agar diffusion method against E. coli and S. aureus, and compared with those of petroleum‐based metal containing polyurethanes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Studies on self cured zinc-containing Pongamia glabra oil based polyesteramide

Efforts have been made for the development of high performance protective coating materials from non drying oil such as Pongamia glabra oil and their commercialization. Zn-containing self cured Pongamia glabra oil based polyesteramide [Zn-APGPEA] resin was synthesized in situ by the reaction of Pongamia glabra fatty amide diol [HEPGA], poly(styrene-co-maleic anhydride) [SMA] and zinc acetate (different ratios) at 100 ± 5 °C in the presence of an acid catalyst. The physico-chemical characterizations of the resin were carried out by standard laboratory methods. The structural elucidation of the prepared resin was carried out by FTIR, ¹H NMR and ¹³C NMR spectral techniques. The thermal behavior was studied by TGA technique. Antibacterial activity was measured by agar diffusion method against Escherichia coli and Staphylococcus aureus. The effect of the loading of zinc on properties of Zn-APGPEA film was also investigated. The properties of Zn-APGPEA compared with reported self cured Pongamia glabra polyesteramide [APGPEA]. Physico-mechanical and chemical/corrosion resistance test of Zn-APGPEA coatings showed that the presence of zinc metal in APGPEA considerably enhances the overall film performance and also improves antibacterial activity. Therefore, Zn-APGPEA can be used as an anti-corrosive and antibacterial coatings material which may substitute polymers obtained from petroleum.     

Studies on self cured zinc-containing Pongamia glabra oil based polyesteramide

Efforts have been made for the development of high performance protective coating materials from non drying oil such as Pongamia glabra oil and their commercialization. Zn-containing self cured Pongamia glabra oil based polyesteramide [Zn-APGPEA] resin was synthesized in situ by the reaction of Pongamia glabra fatty amide diol [HEPGA], poly(styrene-co-maleic anhydride) [SMA] and zinc acetate (different ratios) at 100 ± 5 °C in the presence of an acid catalyst. The physico-chemical characterizations of the resin were carried out by standard laboratory methods. The structural elucidation of the prepared resin was carried out by FTIR, ¹H NMR and ¹³C NMR spectral techniques. The thermal behavior was studied by TGA technique. Antibacterial activity was measured by agar diffusion method against Escherichia coli and Staphylococcus aureus. The effect of the loading of zinc on properties of Zn-APGPEA film was also investigated. The properties of Zn-APGPEA compared with reported self cured Pongamia glabra polyesteramide [APGPEA]. Physico-mechanical and chemical/corrosion resistance test of Zn-APGPEA coatings showed that the presence of zinc metal in APGPEA considerably enhances the overall film performance and also improves antibacterial activity. Therefore, Zn-APGPEA can be used as an anti-corrosive and antibacterial coatings material which may substitute polymers obtained from petroleum.     

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.     

Development and characterization of vinylated polyesteramide from non-edible seeds oils

Annona squamosa- and Pongamia glabra-based polyesteramides (ASPEA and PGPEA) have been reported as corrosion protective coatings. To improve their film properties such as curing, physico-mechanical and anticorrosive properties further, post-vinylation of these resins with styrene and vinyl acetate monomer in varying ratio (4:1, 3:1 and 2:1) was carried out in the presence of free radical initiator (benzoyl peroxide). The incorporation of styrene and vinyl acetate in ASPEA/PGPEA was confirmed by FTIR and ¹H NMR spectral techniques. Physico-chemical, physico-mechanical and anticorrosive properties were studied by standard methods. Thermal stability and curing behaviour of vinylated ASPEA/PGPEA was studied by thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques. It has been observed that vinylation of these resins improves the curing, physico-mechanical and anticorrosive performance of ASPEA/PGPEA films. Among all 2:1 ASPEA/PGPEA:styrene/vinyl acetate ratio exhibited best results.     

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.     

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     

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     

High performance moisture cured poly(ether–urethane) amide coatings based on renewable resource (cottonseed oil)

In this investigation, polyetheramide resin was prepared through the condensation polymerization of N,N-bis (2-hydroxyethyl) cottonseed oil fatty amide (HECOFA) with bisphenol-A. It was further modified by 2,4-toluene diisocyanate (TDI) in 10–30 wt% of polyetheramide to develop a series of moisture curing urethane-modified polyetheramide resins (UMCOPEtA). The synthesized resin was characterized using ¹H NMR, ¹³C NMR, FTIR and solubility in various organic solvents at room temperature. The thermal and curing behavior of the resin was investigated using thermogravimetric analysis and differential scanning calorimetric techniques. The physico-chemical properties such as hydroxyl value, iodine value, specific gravity and mechanical properties like scratch hardness, impact, and flexibility were determined by standard laboratory methods. Coatings of UMCOPEtA resin were prepared on mild steel panels to evaluate chemical resistance performance against acid, alkali, water and xylene. The newly developed UMCOPEtA coatings showed improved hardness, impact, gloss, water and chemical resistance when compared with unmodified polyetheramide coatings, and thus were found to be suitable as a high performance coating material.     

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     

Novel network polymer electrolytes containing fluorine and sulfonic acid lithium prepared by ultraviolet polymerization

Poly(vinyl alcohol) (PVAL) and vinyl acetate‐vinyl alcohol copolymers (VAVAL) were esterified with 3,5‐dinitrobenzoyl chloride using the cycled urea N,N′‐dimethylpropyleneurea (1,3‐dimethyl‐3,4,5,6‐tetrahydro‐2(1H)‐pyrimidinone) (DMPU) as the solvent. Vinyl alcohol‐vinyl‐3,5‐dinitrobenzoate copolymers (VALVDNB) and vinyl acetate‐vinyl‐3,5‐dinitrobenzoate copolymers (VAVDNB) were obtained. High degrees of esterification were obtained when PVAL was esterified (86%). The degree of transformation was determined by ¹H‐NMR as well as by chemical analysis, and the structure of the resulting polymers by means of IR spectroscopy and ¹H‐ and ¹³C‐NMR. The microstructure of PVA, PVAL, VAVAL copolymers and VALVDNB copolymers were determined from ¹H‐ and ¹³C‐NMR techniques. The sequence distributions for VAVAL copolymers prepared by base‐catalyzed transesterification of PVA were blocky, while the distributions were close to random for VALVDNB copolymers obtained by esterification of PVAL. Thermal properties were studied by DSC. The T_g values of VAVAL, VALVDNB, and VAVDNB copolymers as a function of copolymer compositions were determined. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of reactive soybean oils for use as a biobased thermoset resins in structural natural fiber composites

Biobased thermosets resins were synthesized by functionalizing the triglycerides of epoxidized soybean oil with methacrylic acid, acetyl anhydride, and methacrylic anhydride. The obtained resins were characterized with FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy to confirm the functionalization reactions and the extent of epoxy conversion. The viscosities of the methacrylated soybean oil resins were also measured for the purpose of being used as a matrix in composite applications. The cross‐linking capability was estimated by UV and thermally initiated curing experiments, and by DSC analysis regarding the degree of crosslinking. The modifications were successful because up to 97% conversion of epoxy group were achieved leaving only 2.2% of unreacted epoxy groups, which was confirmed by ¹H‐NMR. The ¹³C‐NMR confirms the ratio of acetate to methacrylate methyl group to be 1 : 1. The viscosities of the methacrylated soybean oil (MSO) and methacrylic anhydride modified soybean oil (MMSO) were 0.2 and 0.48 Pas, respectively, which indicates that they can be used in resin transfer molding process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Pyridine-poly(urethane ester amide) coatings from linseed oil

A novel attempt has been made to develop the room temperature cured polyesteramide resin by condensation polymerization reaction between fatty amide diol (N,N-bis 2-hydroxy ethyl linseed oil fatty amide) obtained from oil of linseed (Linum ussitatissimum seeds) and pyridine dicarboxylic acid (PyA) to develop pyridine polyesteramide (Py-PEA), which was further treated with toluylene-2,4-diisocyanate (TDI), in different weight percentages to develop a series of pyridine poly(urethane esteramide) resins (Py-UPEA). The structural elucidation of Py-PEA and Py-UPEA were carried out by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. Physico-chemical characterizations of these resins were performed by standard laboratory methods. Thermal analyses of these resins were accomplished by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques. Coatings of Py-UPEA were prepared on mild steel strips to evaluate their physico-mechanical and chemical/corrosion resistance performances under various corrosive environments. It was found that among all these systems, the sample having 14 wt% loading of TDI showed the best physico-mechanical and corrosion resistance performances. Thermal stability performance suggest that the system could be safely used up to 200 °C.     

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     

Synthesis and characterization of copolymers of bromoacrylated methyl oleate

In this study, methyl oleate was bromoacrylated in the presence of N‐bromosuccinimide and acrylic acid in one step. Homopolymers and copolymers of bromoacrylated methyl oleate (BAMO) were synthesized by free radical bulk polymerization and photopolymerization techniques. Azobisisobutyronitrile (AIBN) and 2,2‐dimethoxy‐2‐phenyl‐acetophenone were used as initiators. The new monomer BAMO was characterized by FTIR, GC‐MS, ¹H, and ¹³C‐NMR spectroscopy. Styrene (STY), methylmethacrylate (MMA), and vinyl acetate (VA) were used for copolymerization. The polymers synthesized were characterized by FTIR, ¹H‐NMR, ¹³C‐NMR, and differential scanning calorimetry (DSC). Molecular weight and polydispersities of the copolymers were determined by GPC analysis. Ten different feed ratios of the monomers STY and BAMO were used for the calculation of reactivity ratios. The reactivity ratios were determined by the Fineman–Ross and Kelen–Tudos methods using ¹H‐NMR spectroscopic data. The reactivity ratios were found to be r_sty = 0.891 (Fineman–Ross method), 0.859 (Kelen–Tudos method); r_bamo = 0.671 (Fineman–Ross method), 0.524 (Kelen–Tudos method). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2475–2488, 2004     

Studies on newly developed urethane modified polyetheramide coatings from Albizia benth oil

Polyetheramide resin based on the condensation polymerisation of N-N-bis (2-hydroxyethyl) Albizia benth oil fatty amide with bisphenol-A was synthesized. The polyetheramide was further modified with urethane linkage resulting from the addition reaction of free hydroxyl groups of the hydroxylethyl Albizia benth oil fatty amide and the isocyanate moeity of toluene 2,4 di-isocyanate. The spectroscopic characterisation (FT-IR, ¹H NMR, ¹³C NMR) as well as the thermal, physicochemical and coating properties of the polyetheramide and its urethaned modified derivatives were carried out. Urethanation led to curing at lower temperature, increase in glass transition and improvement in coating properties and resistance to chemical corrosion.     

Synthesis and characterization of unsaturated polyesters based on the aminolysis of poly(ethylene terephthalate)

The depolymerization of poly(ethylene terephthalate) via an aminolysis process was studied. An excess of ethanol amine in the presence of sodium acetate as a catalyst was used to produce bis(2‐hydroxyl ethylene) terephthalamide (BHETA). Unsaturated polyester (UP) resins were obtained by the reaction of BHETA with different long‐chain dibasic acids such as decanedioic acid, tetradecanoic acid, and octadecanoic acid in conjunction with maleic anhydride as a source of unsaturation. The chemical structure of the UP resins was confirmed by ¹H‐NMR. The vinyl ester resins were used as crosslinking agents for UP. The curing behavior and mechanical properties of the UP resins with vinyl ester were evaluated at different temperatures ranging from 25 to 55°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Synthesis and ultraviolet‐curing behaviors of vinyl ether functionalized polyurethane oligomers

The vinyl ether functionalized oligomer is one of the most basic components of vinyl ether functionalized materials for cationic UV‐curable coatings. In this study, three types of vinyl ether functionalized polyurethane oligomers (i.e., polyether, polyester, and polydimethylsiloxane) were synthesized with diisocyanate, diol, and hydroxyethyl vinyl ether. These oligomers were characterized by IR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. The effect of the raw material ratio on the oligomer, UV‐curing behaviors, and thermal properties of these oligomers were investigated. The UV‐curing behavior was analyzed by real‐time Fourier transform infrared spectroscopy. The vinyl ether terminated polyester urethane oligomer exhibited better UV curing, with a higher final conversion and maximum UV‐curing rates. In addition, the light intensity was enhanced for oligomers with better UV‐curing properties. Research on these vinyl ether functionalized oligomers is essential to the development and applications of cationic vinyl ethers systems. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40501.     

Synthesis and characterization of new vinyl acetate grafting onto epoxidized linseed oil in aqueous media

Modified poly (vinyl acetate) copolymers with epoxidized linseed oil (ELO) as co‐monomer have been prepared. The polymerization was performed in aqueous medium without any additional protective colloid in the presence of sodium persulfate as catalyst. The effect of vinyl acetate (VAc)/ELO feed ratio, reaction temperature, reaction time, and catalyst amount has been studied. FTIR spectroscopy showed that the reaction between ELO and VAc resulted in slight decrease and shift in ELO characteristic bands of oxirane groups; and new bands were detected in the copolymer spectra attributed to PVAc and ELO functional groups. Moreover, new signals attributable to the copolymer were observed in the ¹H NMR spectra (δ 4.07 and 1.62 ppm) and in the ¹³C NMR spectra (δ 15.29 and 31.0 ppm). Analysis by differential scanning calorimetry (DSC) showed a single T_g for the copolymerization product of VAc and ELO and two T_g for the PVAc/ELO blend, indicating the chemical reaction between VAc and ELO. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42089.