Effect of lactic acid chain length on thermomechanical properties of star‐LA‐xylitol resins and jute reinforced biocomposites

Star‐shaped bio‐based resins were synthesized by direct condensation of lactic acid (LA) with xylitol followed by end‐functionalizing of branches by methacrylic anhydride with three different LA chain lengths (3, 5 and 7). The thermomechanical and structural properties of the resins were characterized by ¹³C NMR, Fourier transform IR spectroscopy, rheometry, DSC, dynamic mechanical analysis (DMA), TGA and flexural and tensile tests. An evaluation of the effect of chain length on the synthesized resins showed that the resin with five LAs exhibited the most favorable thermomechanical properties. Also, the resin's glass transition temperature (103 °C) was substantially higher than that of the thermoplast PLA (ca 55 °C). The resin had low viscosity at its processing temperature (80 °C). The compatibility of the resin with natural fibers was investigated for biocomposite manufacturing. Finally, composites were produced from the n5‐resin (80 wt% fiber content) using jute fiber. The thermomechanical and morphological properties of the biocomposites were compared with jute‐PLA composites and a hybrid composite made of the impregnated jute fibers with n5 resin and PLA. SEM and DMA showed that the n5‐jute composites had better mechanical properties than the other composites produced. Inexpensive monomers, good thermomechanical properties and good processability of the n5 resin make the resin comparable with commercial unsaturated polyester resins. © 2017 Society of Chemical Industry     

Synthesis and characterization of bio‐based thermosetting resins from lactic acid and glycerol

A bio‐based thermoset resin has been synthesized from glycerol reacted with lactic acid oligomers of three different chain lengths (n): 3, 7, and 10. Lactic acid was first reacted with glycerol by direct condensation and the resulting branched molecule was then end‐functionalized with methacrylic anhydride. The resins were characterized by Fourier‐transform infrared spectroscopy (FT‐IR), by ¹³C‐NMR spectroscopy to confirm the chemical structure of the resin, and by differential scanning calorimetry and dynamic mechanical thermal analysis (DMTA) to obtain the thermal properties. The resin flow viscosities were also measured using a rheometer with different stress levels for each temperature used, as this is an important characteristic of resins that are intended to be used as a matrix in composite applications. The resin with a chain length of three had better mechanical, thermal, and rheological properties than the resins with chain lengths of seven and 10. Also, its bio‐based content of 78% and glass transition temperature of 97°C makes this resin comparable to commercial unsaturated polyester resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40488.     

Synthesis of rosin‐based flexible anhydride‐type curing agents and properties of the cured epoxy

BACKGROUND: Although rosin acid derivatives have received attention in polymer synthesis in recent years, to the best of our knowledge, they have rarely been employed as epoxy curing agents. The objective of the study reported here was to synthesize rosin‐based flexible anhydride‐type curing agents and demonstrate that the flexibility of a cured epoxy resin can be manipulated by selection of rosin‐based anhydride‐type curing agents with appropriate molecular rigidity/flexibility. RESULTS: Maleopimarate‐terminated low molecular weight polycaprolactones (PCLs) were synthesized and studied as anhydride‐type curing agents for epoxy curing. The chemical structures of the products were confirmed using ¹H NMR spectroscopy and Fourier transform infrared spectroscopy. Mechanical and thermal properties of the cured epoxy resins were studied. The results indicate that both the epoxy/anhydride equivalent ratio and the molecular weight of PCL diol play important roles in the properties of cured resins. CONCLUSION: Rosin‐based anhydride‐terminated polyesters could be used as bio‐based epoxy curing agents. A broad spectrum of mechanical and thermal properties of the cured epoxy resins can be obtained by varying the molecular length of the polyester segment and the epoxy/curing agent ratio. Copyright © 2009 Society of Chemical Industry     

Fatty acid‐based comonomers as styrene replacements in soybean and castor oil‐based thermosetting polymers

In this study, a fatty acid‐based comonomer is employed as a styrene replacement for the production of triglyceride‐based thermosetting resins. Styrene is a hazardous pollutant and a volatile organic compound. Given their low volatility, fatty acid monomers, such as methacrylated lauric acid (MLA), are attractive alternatives in reducing or eliminating styrene usage. Different triglyceride‐derived cross‐linkers resins were produced for this purpose: acrylated epoxidized soybean oil (AESO), maleinated AESO (MAESO), maleinated soybean oil monoglyceride (SOMG/MA) and maleinated castor oil monoglyceride (COMG/MA). The mechanical properties of the bio‐based polymers and the viscosities of bio‐based resins were analyzed. The viscosities of the resins using MLA were higher than that of resins with styrene. Decreasing the content of MLA increased the glass transition temperature (T_g). In fact, the T_g of bio‐based resin/MLA polymers were on the order of 60°C, which was significantly lower than the bio‐based resin/styrene polymers. Ternary blends of SOMG/MA and COMG/MA with MLA and styrene improved the mechanical properties and reduced the resin viscosity to acceptable values. Lastly, butyrated kraft lignin was incorporated into the bio‐based resins, ultimately leading to improved mechanical properties of this thermoset but with unacceptable increases in viscosity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and properties of fluorinated biphenyl‐type epoxy resin

A novel fluorinated biphenyl‐type epoxy resin (FBE) was synthesized by epoxidation of a fluorinated biphenyl‐type phenolic resin, which was prepared by the condensation of 3‐trifluoromethylphenol and 4,4′‐bismethoxymethylbiphenyl catalyzed in the presence of strong Lewis acid. Resin blends mixed by FBE with phenolic resin as curing agent showed low melt viscosity (1.3–2.5 Pa s) at 120–122°C. Experimental results indicated that the cured fluorinated epoxy resins possess good thermal stability with 5% weight loss under 409–415°C, high glass‐transition temperature of 139–151°C (determined by dynamic mechanical analysis), and outstanding mechanical properties with flexural strength of 117–121 MPa as well as tensile strength of 71–72 MPa. The thermally cured fluorinated biphenyl‐type epoxy resin also showed good electrical insulation properties with volume resistivity of 0.5–0.8 × 10¹⁷ Ω cm and surface resistivity of 0.8–4.6 × 10¹⁶ Ω. The measured dielectric constants at 1 MHz were in the range of 3.8–4.1 and the measured dielectric dissipation factors (tan δ) were in the range of 3.6–3.8 × 10^?3. It was found that the fluorinated epoxy resins have improved dielectric properties, lower moisture adsorption, as well as better flame‐retardant properties compared with the corresponding commercial biphenyl‐type epoxy resins. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterisation of star branched polyesters with dendritic cores and the effect of structural variations on zero shear rate viscosity

A series of branched polyesters consisting of poly(ε-caprolactone) (PCL) (degree of polymerisation: 5-200) initiated from hydroxy-functional cores and end-capped with methylmethacrylate have been prepared. The cores were third-generation hyperbranched polyester, Boltorn, with approximately 32 hydroxyl groups, a third-generation dendrimer with 24 hydroxyl groups and a third-generation dendron with eight hydroxyl groups. Finally, a linear PCL was synthesised as a reference material. All initiators were based on 2,2-bis(methylol) propionic acid (bis-MPA). ¹³C NMR spectra of the polymers showed that those with shorter arms contained unreacted hydroxyl groups on the core. Rheological measurements of zero shear rate viscosity, η₀, showed that the branched polyesters had a considerably lower η₀ than linear polyester with similar molecular weight. The low melt viscosity and the crystallity produced a rheological behaviour suitable for the film formation process for powder coatings. Measurements of mechanical properties of cured films showed that those with low arm molecular weight, M_a, were amorphous while those of high M_a were crystalline.     

Effect of molecular weight and content of PDMS on morphology and properties of silicone‐modified epoxy resin

To achieve a stable blend of a bisphenol A type epoxy resin and poly(dimethylsiloxane) (PDMS), reaction between hydroxyl (OH) groups of the epoxy and silanol groups of hydroxyl‐terminated(HT) PDMS has been investigated. The chemical structures of the HTPDMS‐modified epoxies were characterized by Fourier transform infrared (FTIR) and ¹H‐ and ¹³C‐NMR spectroscopy. To allow further understanding of the influence of viscosity and content of HTPDMS on the blend morphology, four different viscosities of HTPDMS were used in three content levels. The morphologies of modified epoxy resins were observed with optical microscopy. The modified epoxies were cured with a cycloaliphatic polyamine. The morphologies of modified epoxies were investigated by using scanning electron microscopy (SEM)/energy dispersive X‐ray (EDX) technique. The cured films showed droplet in matrix morphology with different mean droplets size which was influenced by the viscosity and the content of the incorporated HTPDMS. To illustrate the effect of the morphologies of the cured samples on mechanical properties, tensile strength tests were performed. The introduction of HTPDMS into the epoxy altered the tensile behavior according to its viscosity and content. Surface properties of the cured films were evaluated by sessile drop method. The results clearly indicate that the hydrophilic surface of the epoxy turns to a hydrophobic one due to the modification with HTPDMS. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Synthesis and characterization of novel hydroxyl-terminated N?N–bonded resins

Novel resins containing carbonyl or thiocarbonyl moiety; N N bonds; ethereal linkage; and terminal hydroxyl groups, that is, bis(bisvanillincarbonohydrazone-4′-oxy)butane 1,4-diyldiether and bis(bisvanillinthiocarbonohydrazone-4′-oxy)butane 1,4-diyldiether, have been synthesized by condensing bisvanillincarbono- and bisvanillinthiocarbono-hydrazone, respectively, with 1,4-dibromobutane. The resins were characterized by elemental and hydroxyl equivalent analyses, infrared and ¹H– and ¹³C–NMR spectra, and other properties relevant to their use as propellant binders, such as calorific value, thermal analysis, viscosity, and burning rate measurements. Both these resins have convenient viscosity, indicating their suitability as binders for processing high solid loading, at slightly above room temperature. The resins could be cured easily with toluene diisocyanate and glycerol. The DTA–TG data show that the cured samples start to decompose exothermically at relatively low temperatures, in the range around 160°C. The resins ignite immediately on coming in contact with pure nitric acid, indicating their hypergolic nature. The burning rates of the ammonium perchlorate–based propellant compositions having these resins as binders are much higher than those processed with a conventional butadiene binder. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3204–3211, 2001     

Six‐arm star‐shaped polymer with cyclophosphazene core and poly(ε‐caprolactone) arms as modifier of epoxy thermosets

A six‐arm star‐shaped poly(ε‐caprolactone) (s‐PCL) based on cyclophosphazene core was obtained by presynthesis of a hydroxy‐teminated cyclophosphazene derivative and subsequent initiation of the ring‐opening polymerization of ε‐caprolactone, and its use in different proportions as toughening modifier of diglycidylether of bisphenol A/anhydride thermosets was studied. The star‐shaped polymer was characterized to have approximately 30 caprolactone units per arm. Differential scanning calorimetry revealed a nonsignificant influence on the curing process of the epoxy‐anhydride formulation by the addition of s‐PCL. The s‐PCL‐modified epoxy thermosets exhibited a great improvement in both toughness and strength compared with the neat resin, as the result of a joint effort by the internal rigid core and the external ductile polyester chains of s‐PCL. When the addition of the modifier was 3 wt %, an optimal mechanical and thermomechanical performance was achieved. The impact resistance and tensile strength of the cured epoxy resin were enhanced by 150% and 30%, respectively. The glass transition temperature was also increased slightly. Moreover, the addition of the star‐shaped modifier had little harmful effect on the thermal stability of the material. Thus s‐PCL was proved to be a superior toughening agent without sacrificing thermal and mechanical properties of the thermosets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44384.     

Renewably sourced phenolic resins from lignin bio‐oil

Traditional lignin pyrolysis generates a bio‐oil with a complex mixture of alkyl‐functionalized guaiacol and syringol monomers that have limited utility to completely replace phenol in resins. In this work, formate assisted fast pyrolysis (FAsP) of lignin yielded a bio‐oil consisting of alkylated phenol compounds, due to deoxyhydrogenation, that was used to synthesize phenol/formaldehyde resins. A solvent extraction method was developed to concentrate the phenolics in the extract to yield a phenol rich monomer mixture. Phenolic resins were synthesized using phenol (phenol resin), FAsP bio‐oil (oil resin), and an extract mimic (mimic resin) that was prepared to resemble the extract after further purification. All three phenolic sources could synthesize novolac resins with reactive sites remaining for subsequent resin curing. Differential scanning calorimetry and thermogravimetric analysis of the three resins revealed similar thermal and decomposition behavior of phenol and the mimic resins, while the oil resin was less stable. Resins were cured with hexamethylenetetramine and the mimic resin demonstrated improved curing energies compared to the oil resin. The adhesive strength of the mimic resin was found to be superior to that of the oil resins. These results confirmed that extracting a mixture of substituted aromatics from FAsP bio‐oil could synthesize resins with properties similar to those from phenol and improved over the parent bio‐oil. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44827.     

Soybean and castor oil based monomers: Synthesis and copolymerization with styrene

In this study, castor oil was alcoholyzed with both aliphatic alcohols, such as glycerol and pentaerythritol, and an aromatic alcohol, bisphenol A propoxylate. The resulting alcoholysis products were then malinated and cured in the presence of styrene. Soybean oil pentaerythritol glyceride maleates were also prepared for a direct comparison of the properties of the castor oil and soybean oil based resins. Castor oil was directly malinated as well to see the effect of the alcoholysis step on the properties of the castor oil based resins. The monomers synthesized were characterized by ¹H‐NMR spectroscopy, and the styrenated resin liquid properties, such as viscosity and surface energy values, were determined. The conversion of polymerization was determined using time resolved FTIR analysis for the styrenated soybean oil pentaerythritol glyceride maleates, castor oil maleates, and castor oil pentaerythritol glyceride maleates. The effect of monomer identity and styrene content on the conversion of polymerization was explored. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2433–2447, 2006     

Mesua ferrea L. seed oil‐based epoxy resins

Exhaustion of fossil fuels, tremendous increase of materials demand, and unpredictable prices of petroleum based products urge upon the sustainable development. Three different epoxy resins have been synthesized from monoglyceride of Mesua ferrea L. seed oil and epichlorohydrin with and without other dihydroxy compound like tetrabromobisphenol‐A (TBPA) and bisphenol‐A (BPA). The synthesized epoxy resin were characterized by measurement of physical properties like epoxy equivalent, viscosity, hydroxyl value, saponification value, acid value, etc., and spectroscopic techniques like FTIR and ¹H NMR. High thermostability with initial decompositions temperature of 225–265°C was observed for the cured resins and 75 mol % BPA based resin exhibits the highest thermostability. Newtonian flow behavior was observed for all resins as indicated by the rheometric study (CVO 100). The flame retardency rating of TBPA based epoxy was found to be V1 as tested by UL 94. The performance characteristics as coating materials were studied by the measurement of gloss, impact resistance, scratch hardness, tensile strength, elongation at break, adhesive strength, and chemical resistance. The results indicate the suitability of the synthesized resins as coating materials. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mahua‐oil‐based resins for the high‐temperature curing of fly ash coatings

We attempted to prepare medium‐oil‐length glycerol alkyds based on Mahua oil. Fatty acids were isolated from the oil and used in the preparation of alkyds by the fusion method. The resins were characterized by IR spectroscopic analysis. The physicochemical and film properties of these resins were also studied. IR analysis of the resins revealed the formation of phthalate esters showing characteristic peaks at 1720 cm^?1. The resin was modified with melamine formaldehyde, which cured at high temperatures. Alternatively, the resin was made to air dry with ester gum, and the curing behavior was studied. The suitability of these resins for high‐temperature curing fly ash coating applications was established. Coatings were formulated with these resins and with 40% fly ash as an extender. The coatings were characterized by standard techniques, particularly for their anticorrosive and antiabrasive properties. Resistance to corrosion was evaluated in humidity and in salt‐spray conditions. We conducted a high‐stress (two‐body) abrasion test to test the abrasive wear resistance of the coatings. The Mahua‐oil‐resin‐based fly ash coatings were suitable for application in moderately corrosive and abrasive environments. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 110–120, 2003     

Biobased epoxy resin from canola oil

Epoxidized canola oil (ECO)‐based thermoset epoxy resins were formulated with phthalic anhydride (PA) as the curing agent for different ratios of ECO to PA (1:1, 1:1.5, and 1:2 mol/mol) at curing temperatures of 155, 170, 185, and 200°C. The gelation process of the epoxy resins and the viscoelastic properties of the systems during curing were studied by rheometry, whereas the dynamic mechanical and thermal properties of the cured resins were studied by dynamic mechanical analysis (DMA) and differential scanning calorimetry. We found that the thermomechanical properties of the resins were not strongly dependent on the curing temperature of the resin, although elevated temperatures significantly accelerated the curing process. However, an increase in the curing agent (PA) amount significantly altered both the reaction rate and the thermomechanical properties of the final resin. Thus, in the ECO/PA system, the selection of the combination of the curing temperature and the molar ratios of the curing agent could be used to design thermoset resins with unique thermomechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40142.     

Modification of melamine‐formaldehyde resins by substances from renewable resources

In the present contribution, investigations on the chemical modification of thermosetting melamine formaldehyde resins by natural polyol compounds are presented. As representative agents soluble starch, sucrose, and glycerol were chosen to cover three different classes of polyols. The major aim was to use substances produced from natural bio‐renewable feedstock that are available in large quantities and may serve as environmentally innocuous and bio‐renewable substitutes for petro‐chemically derived and potentially hazardous materials. Different reaction conditions lead to resins with varying technical performance. For soluble starch no reaction conditions could be found that allow the adoption of this substitute for the laminate industry due to insufficient technological performance. Sucrose and glycerol on the other hand yielded impregnation resins with suitable performance. Chemical linkage of the modifying agent into the chain propagation by poly‐condensation however, was only found with glycerol. The covalent incorporation of glycerol in the network was observed with addition of glycerol at different stages during synthesis. The technological performance of the various modified thermosetting resins was assessed by determining flow viscosity, molar mass distribution, the storage stability, and in a second step laminating impregnated paper to particle boards and testing the resulting surfaces according to standardized quality tests. Spectroscopic evidence of chemical incorporation of glycerol was found by applying by ¹H, ¹³C, ¹H/¹³C HSQC, ¹H/¹³C HMBC, and ¹H DOSY methods. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and Characterization of a Novel Low‐Viscosity Unsaturated Hyperbranched Polyester Resin

Hyperbranched thermosetting resin is the best additive for toughening and reinforcing linear thermosetting resin. A novel low‐viscosity unsaturated hyperbranched polyester resin (UHPR) is synthesized by the reaction between maleic anhydride monoisooctyl alcohol ester and a hydroxyl‐ended hyperbranched polyester resin (HPR) prepared from phthalic anhydride (PA) and trimethylolpropane (TMP). The structure of HPR is characterized by FT‐IR and ¹H NMR, and its degree of branching is deduced by comparing with the ¹H NMR spectrum of a model compound. The molecular weights of HPR and UHPR are determined by theoretical calculation and MALDI‐TOF MS measurements. This low‐viscosity (< 10 000 cP) novel UHPR can be applied in the field of environment‐friendly coatings and in toughening and reinforcing linear unsaturated polymers.     

Mechanical characterization and chemical resistances of cured unsaturated polyester resins modified with vinyl ester resins based on recycled poly(ethylene terephthalate)

Unsaturated polyester resin (UP) was prepared from glycolyzed oligomer of poly(ethylene terephthalate) (PET) waste based on diethylene glycol (DEG). New diacrylate and dimethacrylate vinyl ester resins prepared from glycolysis of PET with tetraethylene glycol were blended with UP to study the mechanical characteristics of the cured UP. The vinyl ester resins were used as crosslinking agents for unsaturated polyester resin diluted with styrene, using free‐radical initiator and accelerator. The mechanical properties of the cured UP resins were evaluated. The compressive properties of the cured UP/styrene resins in the presence of different vinyl ester concentrations were evaluated. Increasing the vinyl ester content led to a pronounced improvement in the compression strength. The chemical resistances of the cured resins were evaluated through hot water, solvents, acid, and alkali resistance measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3175–3182, 2007     

High‐performance thermosets with tailored properties derived from methacrylated eugenol and epoxy‐based vinyl ester

A renewable chemical, eugenol, is methacrylated to produce methacrylated eugenol (ME) employing the Steglich esterification reaction without any solvent. The resulting ME is used as a low‐viscosity co‐monomer to replace styrene in a commercial epoxy‐based vinyl ester resin (VE). The volatility and viscosity of ME and styrene are compared. The effect of ME loading and temperature on the viscosity of the VE–ME resin is investigated. Moreover, the thermomechanical properties, curing extent and thermal stability of the fully cured VE–ME thermosets are systematically examined. The results indicate that ME is a monomer with low volatility and low viscosity, and therefore the incorporation of ME monomer in VE resins allows significant reduction of viscosity. Moreover, the viscosity of the VE–ME resin can be tailored by adjusting the ME loadings and processing temperature to meet commercial liquid molding technology requirements. The glass transition temperatures of VE–ME thermosets range from 139 to 199 °C. In addition, more than 95% of the monomer is incorporated and fixed in the crosslinked network structure of VE–ME thermosets. Overall, the developed ME monomer exhibits promising potential for replacing styrene as an effective low‐viscosity co‐monomer. The VE–ME resins show great advantages for use in polymer matrices for high‐performance fiber‐reinforced composites. This work is of great significance to the vinyl ester industry by providing detailed experimental support. © 2018 Society of Chemical Industry     

Chain-extended bismaleimides. II. A study of chain-extended bismaleimides as matrix elements in carbon fiber composites

A series of chain-extended bismalemide resins as matrix elements in carbon fibers were cured and characterized in terms of their thermal and thermomechanical properties. The cured resins were stable up to 430°C and EDABMI/MDA has the highest T^g value and the lowest loss modulus value. To understand the compatibility and the degree of adhesion between the resin and the fiber, their surface properties were determined in terms of the surface energy component and single-fiber pull-out tests. The surfaces of the resins were found to have a basic character. The resins containing ether groups have a higher degree of basicity than does the resin containing methylene groups. Similarly, an increasing trend in the interlaminar shear strength (ILSS) and the work of adhesion values were observed with the increasing number of the ether groups in the resin structure. © 1996 John Wiley & Sons, Inc.     

Structure–property correlations of flexible clear coats

In this paper thermomechanical and mechanical properties of various free clear coat films for coil-coated steel sheets were studied by dynamic mechanical analysis and tensile testing. To establish structure–property correlations, polyacrylate and polyester binder resins with varying molar mass and functionality were investigated. The clear coat films based on polyacrylate binders exhibited higher glass transitions values, crosslinking densities, elastic modulus and tensile strength values. For both resin types, a relationship of the properties glass transition temperature, crosslinking density, stiffness and tensile strength and the functionality considering the molar mass and the hydroxyl value of the resins was obtained. The elastic strain energy of the investigated brittle clear coat films depended mainly on the elastic modulus.