Cure of epoxy novolacs with aromatic diamines. I. Vitrification,gelation, and reaction kinetics

The cure reaction of a commercial epoxidized novolac with 4,4' diaminodiphenylsulfone (DDS) was studied at constant cure temperatures in the range 120–270°C, as well as at constant heating rates (differential scanning calorimetry, DSC). Stoichiometric formulations did not attain complete conversion due to the presence of topological restrictions. The limiting conversion was x_max = 0.8. Samples containing an amine excess (≥ 20%) could be completely reacted, whereas this was not possible for formulations containing an epoxy excess. Samples containing a 20% amine excess showed the maximum value of the glass transition temperature (T_g230°C). Cure took place by epoxy-amine hydrogen reactions catalyzed by (OH) groups. A reactivity ratio of secondary to primary amine hydrogens equal to 0.2 was found. The activation energy was E = 61 kJ/mol, as arising from T_g versus time shift factors and time to gel measurements. A unique relationship between T_g and x could be obtained. Gelation took place at x_gel = 0.45 and the maximum T_g for the stoichiometric system was T_gmax = 215°C for x = 0.8. A conversion versus temperature transformation diagram was used to represent conditions where gelation, vitrification, degradation, and topological limitations took place. © 1993 John Wiley & Sons, Inc.     

Chemical epoxidation of a natural unsaturated epoxy seed oil fromVernonia galamensis and a look at epoxy oil markets

Since 1963, production of all epoxy esters has ranged from 60 to 150 million lb annually, a steady 7% of the 1 to 2 billion lb of annual plasticizer production. Growth rates in production averaged 4.3% for all plasticizers, 3.8% for all epoxy esters and 5.0% for epoxidized soybean oil (ESBO). ESBO accounted for 70–76% of total epoxy ester production (1963–1982). The natural liquid epoxy oil fromVernonia galamensis seed, with oxirane value (4.1%) and viscosity (100 cps) similar to some commercial epoxy fatty esters but with molecular weight similar to epoxidized vegetable oils, combines some of the properties of both commercial types. Chemical epoxidation ofVernonia oil raises the oxirane content to 8.2, intermediate between ESBO and epoxidized linseed oil (ELSO), while consuming less of the costly epoxidizing reagents. Epoxidation proceeds in stepwise fashion through partially epoxidized products, which are converted to final product. Since the major fatty components ofVernonia oil arecis-12,13-epoxy-9-octadecenoic (75%) and linoleic (13%) acids, further epoxidation produces fatty acids that are specifically epoxidized at the 9,10- and 12,13-positions, and the major product has 6 epoxy units per triglyceride molecule. The resulting mixture of products has compositional and physical properties distinctly different from commercial samples of ESBO and ELSO.     

Evaluation of infrared spectroscopic techniques to determine the Drago constants of a cycloaliphatic epoxy

The task of understanding adhesion is not complete without considering acid–base interactions. Such site-specific interactions play a major role in promoting adhesion. However, these interactions are often difficult to characterize or quantify. In this work, a cycloaliphatic epoxy resin is studied by Fourier Transform Infrared (FT-IR) spectroscopy to identify and quantify possible molecular interactions. As controls, simple molecules such as acetone and ethyl acetate were also studied. Moreover, interactions of molecules with structural similarities to the epoxy resin were studied to provide additional insight. Two infrared spectroscopic techniques, carbonyl peak shifts and hydroxyl peak shifts, were employed to quantify the acid–base interactions of these organic molecules. The Drago constants from carbonyl peak shifts were determined from predicted heats of complexation and also directly from hydroxyl peak shifts. The constants obtained for the control molecules were compared with published data. The Drago constants of the control molecules determined by hydroxyl peak shifts agreed well with literature values, in contrast, to those derived from the carbonyl peak shifts. This lack of correlation may be attributed to the influence of solvent effects and concentration dependence on carbonyl shifts. Using the hydroxyl peak shift approach, the Drago constants for the cycloaliphatic epoxy group of cycloaliphatic epoxy resin were found to be E _B = 2.69 (kJ/mol)^1/2 and C _B = 4.04 (kJ/mol)^1/2 and E _B = 3.45 (kJ/mol)^1/2 and C _B = 2.11 (kJ/mol)^1/2 for the ester group of the epoxy resin. The average Drago constants for the resin were found to be E _B = 3.28 ± 0.14 (kJ/mol)^1/2 and C _B = 2.00 ± 0.09 (kJ/mol)^1/2.     

Influence of some vegetable oils on the photocrosslinking of coatings based on an o-cresol novolac epoxy resin and a bis-cycloaliphatic diepoxide

The influence of cashew nut shell oil (CNO), epoxidized soybean oil (ESO), castor oil (CO), and dioctyl phtalate (DOP) on the photocrosslinking kinetics of UV curable mixtures containing an o-cresol novolac epoxy resin (CNE), a bis-cycloaliphatic diepoxide monomer (BCDE), and a triarylsulfonium salt (TAS) as a cationic photoinitiator has been studied. The formulation with a weight ratio CNE/BCDE/TAS of 60/40/5 was found to have the highest cure rate and the greatest final conversion of epoxy groups upon UV exposure. The presence of an unsaturated oil or of DOP in the UV curable formulation, at a content ranging from 0.07 to 0.79 mol/kg, was shown to increase the initial polymerization rate of the epoxy groups from 12 up to 31 mol/kg s, and the epoxy conversion after 18 s UV exposure from 80 up to 95%. It was found that the UV cured coatings containing CNO or DOP at concentrations between 0.3 and 0.6 mol/kg and ESO at concentrations between 0.12 and 0.19 mol/kg exhibit the best performance. These results were explained by a number of competitive factors, mainly the effects of the chemical structure and content of the oils and of DOP on the polarity, viscosity, compatibility, and internal filter effect of the UV curable resins, as well as by the characteristics of the tridimensional polymer networks formed upon UV exposure. The materials produced under the optimal conditions determined in this study can be used as high performance decorative and protective coatings and also as adhesives in different sectors of applications.     

Epoxidized Mesua ferrea L. seed oil-based reactive diluent for BPA epoxy resin and their green nanocomposites

An epoxidized vegetable oil of Mesua ferrea L. seed was prepared and used as a reactive diluent for commercial BPA-based epoxy resin at different compositions for the first time. The prepared epoxidized oil (ENO100) was characterized by determination of physical properties like epoxy equivalent, viscosity, hydroxyl value, saponification value, iodine value, acid value, etc. and FTIR study. The morphology and rheological characteristics of the ENO100 modified commercial epoxy systems have been studied by SEM and rheometer. The performance of poly(amido amine) cured above resin systems have been investigated by the measurement of drying time, tensile strength, elongation at break, adhesive strength, impact resistance, scratch hardness, gloss and chemical resistance studies. The results indicate that the epoxidized oil not only reduces the viscosity of the BPA-based epoxy resin but it also enhances the performance of the cured resin. The performance of this system (50 wt.% dilution) was further enhanced by formation of nanocomposites using ex-situ technique with organically modified nanoclay at different dose levels (1–5 wt.%).The formation of nanocomposites was confirmed by XRD, SEM and FTIR studies. The studies of above performance indicate the enhancement of properties compared to pristine system. As naturally renewable diluent is used in the above studies, so the resultant nanocomposites are green high performance materials with zero VOC.     

Compatibility of liquid deproteinized natural rubber having epoxy group (LEDPNR)/poly (L‐lactide) blend

Reaction after mixing of liquid epoxidized natural rubber/poly(L ‐lactide) blend was performed to enhance the compatibility of the blend. The liquid epoxidized natural rubber was prepared by epoxidation of deproteinized natural rubber with peracetic acid in latex stage followed by depolymerization with peroxide and propanal. The resulting liquid deproteinized natural rubber having epoxy group (LEDPNR) was mixed with poly(L ‐lactide) (PLLA) to investigate the compatibility of the blend through differential scanning calorimetry, optical light microscopy, and NMR spectroscopy. After heating the blend at 473 K for 20 min, glass transition temperature (T_g) of LEDPNR in LEDPNR/PLLA blend increased from 251 to 259 K, while T_g and melting temperature (T_m) of PLLA decreased from 337 to 332 K and 450 to 445 K, respectively, suggesting that the compatibility of LEDPNR/ PLLA blend was enhanced by a reaction between the epoxy group of LEDPNR and the ester group of PLLA. The reaction was proved by high‐resolution solid‐state ¹³C NMR spectroscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of poly(1,4‐cyclohexylenedimethylene phthalate)s and their use as modifiers for aromatic diamine‐cured epoxy resin

Poly(1,4‐cyclohexylenedimethylene phthalate) s, prepared by the reaction of phthalic anhydride and 1,4‐cyclohexane dimethanol (35/65 or 73/27 mol % cis/trans or trans alone), have been used to improve the toughness of bisphenol‐A diglycidyl ether epoxy resin cured with 4,4′‐diaminodiphenyl sulfone. The aromatic polyesters include poly(cis/trans‐1,4‐cyclohexylenedimethylene phthalate) (PCP) based on a commercial cyclohexanedimethanol, poly(trans‐1,4‐cyclohexylenedimethylene phthalate) (trans‐PCP) and poly(cis/trans‐1,4‐cyclohexylenedimethylene phthalate) (cis‐rich PCP) prepared from a cis‐rich diol. The polyesters used were soluble in the epoxy resin without solvents and were effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt% of PCP (MW 6400 g mol⁻¹) led to an 80% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of morphological and dynamic viscoelastic behaviours of the modified epoxy resin system. © 2000 Society of Chemical Industry     

Synthesis and characterization of novel poly(aryl ether ketone)s containing both biphenylene and 1,4-naphthylene moieties

A novel epoxidized hydroxyl-terminated hyperbranched polymer (HPEEX) was formulated from epichlorohydrin and hydroxy-terminated hyperbranched polyester (HPE) based on trimethylol propane (TMP) and AB₂ monomer. The obtained HPEEX was characterized with FT-IR, ¹HNMR spectroscopy, TG, WAXD and GPC analysis. Results showed that the HPEEX was formulated as expected and its molecular weight and intrinsic viscosity were 3,789 g/mol and 3.96 mL/g, respectively. Meanwhile, the HPEEX was used as cross-linking agent in the preparation of waterborne epoxy resins. Performance of the HPEEX modified epoxy resin aqueous (EP-H) dispersions and their films was evaluated by various tests. It was found that with incorporation of hyperbranched polymer into the epoxy macromolecular chain, the EP-H films exhibited excellent hardness and water-proof performance: the hardness was as high as 96 (Shore A), and the contact angle of water on the surface of this kind of film was as high as 71°, resulting from branched structure, higher functionality of HPEEX, better cross-linking density and large number of hydrogen bonding in this epoxy system.     

Cure kinetics and thermal stability of micro and nanostructured thermosetting blends of epoxy resin and epoxidized styrene‐block‐butadiene‐block‐styrene triblock copolymer systems

The compatibility of styrene‐block‐butadiene‐block‐styrene (SBS) triblockcopolymer in epoxy resin is increased by the epoxidation of butadiene segment, using hydrogen peroxide in the presence of an in situ prepared catalyst in water/dichloroethane biphasic system. Highly epoxidized SBS (epoxy content SBS >26 mol%) give rise to nanostructured blends with epoxy resin. The cure kinetics of micro and nanostructured blends of epoxy resin [diglycidyl ether of bisphenol A; (DGEBA)]/amine curing agent [4,4′‐diaminodiphenylmethane (DDM)] with epoxidized styrene‐block‐butadiene‐block‐styrene (eSBS 47 mol%) triblock copolymer has been studied for the first time using differential scanning calorimetry under isothermal conditions to determine the reaction kinetic parameters such as kinetic constants and activation energy. The cure reaction rate is decreased with increasing the concentration of eSBS in the blends and also with the lowering of cure temperature. The compatibility of eSBS in epoxy resin is investigated in detailed by Fourier transform infrared spectroscopy, optical and transmition electron microscopic analysis. The experimental data of the cure behavior for the systems, epoxy/DDM and epoxy/eSBS(47 mol%)/DDM show an autocatalytic behavior regardless of the presence of eSBS in agreement with Kamal's model. The thermal stability of cured resins is also evaluated using thermogravimetry in nitrogen atmosphere. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Epoxidized soybean oil modified using fatty acids as tougheners for thermosetting epoxy resins: Part 2—Effect of curing agent and epoxy molecular weight

A series of bio-rubber (BR) tougheners for thermosetting epoxy resins was prepared by grafting renewable fatty acids with different chain lengths onto epoxidized soybean oil at varying molar ratios. BR-toughened samples were prepared by blending BRs with diglycidyl ether of bisphenol A resins, Epon 828 and Epon 1001F, at different weight fractions and stoichiometrically cured using an amine curing agent, 4, 4′-methylene biscyclohexanamine (PACM). Fracture toughness properties of the unmodified and BR toughened polymer samples—including critical strain energy release rate (G_Ic), and critical stress intensity factor (K_Ic)—were measured to investigate the toughening effect of prepared BRs. It was found that the degree of phase separation and toughening were more controllable relative to similar polymers cured using the aromatic curing agent Epikure W, and the use of higher molecular epoxy resins produces a synergistic effect increasing the toughness much more than similar polymers made with lower molecular weight epoxy resins. Average BR domain sizes ranging from 200 to 900 nm were observed, and formulations with G_Ic, values K_Ic as high as 1.0 kJ/m² and 1.4 MPa m^1/2 were attained respectively for epoxy systems with T_g greater than 130°C.     

Synthesis,characterization, and properties of a novel epoxy resin containing both binaphthyl and biphenyl moieties

A new epoxy resin containing both binaphthyl and biphenyl moieties in the skeleton (BLBPE) was synthesized and confirmed by electrospray ionization mass spectroscopy, ¹H‐nuclear magnetic resonance spectroscopy, and infrared spectroscopy. To evaluate the combined influence of two moieties, one epoxy resin containing binaphthyl moiety and another containing biphenyl moiety were also synthesized, and a commercial biphenyl‐type epoxy resin (CER3000L) was introduced. Thermal properties of their cured polymers with phenol p‐xylene resins were characterized by differential scanning calorimetry, dynamic mechanical, and thermogravimetric analyses. The cured polymer obtained from BLBPE showed remarkably higher glass transition temperature and lower moisture absorption, as well as comprehensively excellent thermal stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Epoxidation of Methanol-Soluble Kraft Lignin for Lignin-Derived Epoxy Resin and Its Usage in the Preparation of Biopolyester

Most commercial epoxy resins have been produced using toxic bisphenol A. Lignin can be utilized as green substitute for bisphenol A to produce bio-epoxy resins. Methanol-soluble kraft lignin was extracted by methanol fractionation for lignin epoxidation, and epoxidized into lignin-derived epoxy resin via two-step epoxidation consisting of epichlorohydrin addition and epoxide ring restructuring. Epoxidized lignin was selectively separated from non- or less-reacted lignin based on their solubility differences in organic solvents. The existence of epoxide groups in the lignin-derived epoxy resin was confirmed using FT-IR, ¹H-NMR, and TGA analyses. Epoxidized lignin was used as a reactive lignin macromonomer to prepare biopolyester. The characteristics of the synthesized biopolyester were analyzed using FT-IR, and the thermal properties were analyzed by TGA. The thermal decomposition temperature of 5% weight loss (T_d5) was determined to be 257.1°C, which is comparable to epoxy resins that are used in electronic applications.     

Synthesis and properties of cross‐linked polymers from epoxidized rubber seed oil and triethylenetetramine

A series of epoxidized oils were prepared from rubber seed, soybean, jatropha, palm, and coconut oils. The epoxy content varied from 0.03 to 7.4 wt %, in accordance with the degree of unsaturation of the oils (lowest for coconut, highest for rubber seed oil). Bulk polymerization/curing of the epoxidized oils with triethylenetetramine (in the absence of a catalyst) was carried out in a batch setup (1 : 1 molar ratio of epoxide to primary amine groups, 100°C, 100 rpm, 30 min) followed by casting of the mixture in a steel mold (180°C, 200 bar, 21 h) and this resulted in cross‐linked resins. The effect of relevant pressing conditions such as time, temperature, pressure, and molar ratio of the epoxide and primary amine groups was investigated and modeled using multivariable nonlinear regression. Good agreement between experimental data and model were obtained. The rubber seed oil‐derived polymer has a T_g of 11.1°C, a tensile strength of 1.72 MPa, and strain at break of 182%. These values are slightly higher than for commercial epoxidized soybean oil (T_g of 6.9°C, tensile strength of 1.11 MPa, and strain at break of 145.7%). However, the comparison highlights the potential for these novel resins to be used at industrial/commercial level. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42591.     

Development and evaluation of pressure sensitive adhesives from a fatty ester

Novel pressure sensitive adhesives (PSAs) were developed from renewable methyl oleate (MO) and fully evaluated for their peel strength, tack force and shear resistance. MO was epoxidized and selectively hydrolyzed on the ester group to form epoxidized oleic acid (EOA) that is a bifunctional monomer containing both a carboxylic acid group and an epoxy group. EOA was step‐growth polymerized to form a hydroxyl‐containing polyester, which was then cured in the presence of a small amount of a polyfunctional epoxide [epoxidized soybean oil or trimethylolpropane triglycidyl ether (TMPTGE)] to afford PSAs. The PSAs from the polyester cured with TMPTGE exhibited high peel strength (2.4 N/10 mm), high tack force (5.8 N), and sufficient shear resistance (9.0 min). The PSAs can be fully based on renewable natural materials, and their preparations are environmentally friendly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41143.     

Electrochemical biosensor for detection of formaldehyde in rain water

BACKGROUD: This study describes the construction of an electrochemical formaldehyde biosensor based on poly(glycidyl methacrylate‐co‐3‐methylthienyl methacrylate)/formaldehyde dehydrogenase/polypyrrole [poly(GMA‐co‐MTM)/FDH/PPy] composite film electrode. Formaldehyde dehydrogenase (FDH) was chemically immobilized via the epoxy groups of the glycidyl methacrylate (GMA) side chain of the polymer. Formaldehyde measurements were conducted in 0.1 mol L^?1, pH 8 phosphate buffer solution (PBS) including 0.1 mol L^?1 KCl, 0.5 mmol L^?1 of NAD⁺ (cofactor of the enzyme) and 1 mmol L^?1 of 1,2‐napthoquinone‐4‐sulfonic acid sodium salt (NQS) as mediator with an applied potential of ? 0.23 V (vs. Ag/AgCl, 3 mol L^?1 NaCl). Analytical parameters of the biosensor were calculated and discussed. The biosensor was tested in rain water samples. RESULTS: Sensitivity was found to be 15 000 per mmol L^?1 (500 nA ppm^?1) in a linear range between 0.1 ppm and 3 ppm (3.3–100 µmol L^?1). A minimum detectable concentration of 4.5 ppb (0.15 µmol L^?1) (S/N = 3) with a relative standard deviation (RSD) of 0.73% (n = 5) was obtained from the biosensor. Response time of the biosensor was very short, reaching 99% of its maximum response in about 4 s. The biosensor was also tested for formaldehyde measurements in rain water samples. Formaldehyde concentrations in samples were calculated using the proposed biosensor with recovery values ranged between 92.2 and 97.7% in comparison with the colorimetric Nash method. CONCLUSION: The poly(GMA‐co‐MTM)/FDH/PPy) electrode showed excellent measurement sensitivity in comparison with other formaldehyde biosensor studies. Strong chemical bonding between the enzyme and the copolymer was created via the epoxy groups of the composite film. The proposed biosensor could be used successfully in rain waters without a pretreatment step. © 2012 Society of Chemical Industry     

Quantitative analysis for reaction between epoxidized natural rubber and poly (L‐lactide) through 1H‐NMR spectroscopy

Reaction between epoxidized natural rubber and poly(L ‐lactide) (PLLA) was investigated quantitatively in terms of conversion of the epoxidized natural rubber. The epoxidized natural rubber was prepared by epoxidation of high ammonia natural rubber (HA‐NR) or deproteinized natural rubber (DPNR) with peracetic acid followed by depolymerization with ammonium persulfate. The resulting liquid HA‐NR having epoxy group (LENR) or liquid DPNR having epoxy group (LEDPNR) were subjected to heating at 473 K for 20 min, after blending with PLLA. The products were characterized through morphology observation, DSC measurement, and ¹H‐NMR spectroscopy. The conversions of the rubbers were estimated from intensity ratio of signals in ¹H‐NMR spectrum for the products after removing unreacted rubber with toluene. Difference in the estimated conversion between the LENR/PLLA and LEDPNR/PLLA blends was interpreted in relation to proteins present in the rubber. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis,characterization, and evaluation of carboxyl‐terminated poly(ethylene glycol) adipate‐modified epoxy networks: Effect of molecular weight

A series of carboxyl‐terminated poly(ethylene glycol) adipate (CTPEGA) was synthesized by polycondensation of poly(ethylene glycol) (PEG) of various molecular weights (“2000,” “4000,” “6000,” “8000,” “10,000” g/mol) and adipic acid. CTPEGA was incorporated into the epoxy by a prereaction method. The CTPEGA and modified epoxy samples were thoroughly characterized by Fourier transform infrared spectroscopy, ¹H NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography. The effects of molecular weight of CTPEGA on thermomechanical and viscoelastic properties of the modified epoxy networks were investigated. Maximum improvement in impact strength was found for the epoxy network modified with CTPEGA containing PEG of molecular weight 2000 g/mol. With further increase in molecular weight of CTPEGA, the impact strength of the modified network decreases. However, in case of higher molecular weight CTPEGA, the improvement in toughness was achieved without any reduction in T_g due to the complete phase separation. The results were explained in terms of morphology studied by scanning electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1723–1730, 2007     

Synthesis and characterization of low viscous and highly acrylated epoxidized methyl ester based green adhesives derived from linseed oil

Both epoxidized linseed oil and transesterified epoxidized linseed oil were acrylated to form UV curable bio-based oligomers. The synthesis was confirmed by FTIR and ¹H NMR and oxirane oxygen content (OOC). The OOC value of epoxidized linseed oil was determined to be 8.2 % which was reduced to 8.0 % after transesterification confirming the retaining of epoxy groups. The lower OOC of acrylated epoxidized linseed oil (AELO) (2.1 %) and acrylated epoxy methyl esters (AEME) (0.9 %) revealed successful acrylation. The degree of acrylation in AEME was higher (~ 90 %) than AELO (~ 77%) and most importantly, the viscosity of AEME was much lower than AELO revealing better processability for industrial use.     

Thermomechanical behavior of epoxy resins modified with epoxidized vegetable oils

Biobased epoxy materials were prepared from diglycidyl ether of bisphenol A (DGEBA) and epoxidized vegetable oils (EVOs) (epoxidized soybean oil and epoxidized castor oil) with a thermally latent initiator. The effects of EVO content on the thermomechanical properties of the EVO‐modified DGEBA epoxy resins were investigated using several techniques. Differential scanning calorimetry indicated that the cure reaction of the DGEBA/EVO systems proceeded via two different reaction mechanisms. Single and composition‐dependent glass transition temperature (T_g) mechanisms were observed for the systems after curing. The experimental values of T_g could be explained by the Gordon–Taylor equation [Gordon M and Taylor JS, J Appl Chem 2 :493 (1952)]. The thermal stability of the systems decreased as the EVO content increased, due to the lower crosslinking density of the DGEBA/EVO systems. The coefficient of thermal expansion of the systems was found to increase linearly with increasing EVO content. This could be attributed to the fact that the degrees of freedom available for motions of the segments of the macromolecules in the network structure were enhanced by the addition of EVO. Copyright © 2008 Society of Chemical Industry