Kinetics and thermodynamics of isothermal curing reaction of epoxy‐4, 4′‐diaminoazobenzene reinforced with nanosilica and nanoclay particles

The kinetics of the cure reaction for a system of bisphenol‐A epoxy resin (DGEBA), with 4, 4′‐diaminoazobenzene (DAAB), reinforced with nanosilica (NS), and nanoclay (NC) by means of isothermal technique of differential scanning calorimetry were studied. The Kamal autocatalytic‐like kinetic model was used to estimate the reaction orders (m, n), rate constants (k₁, k₂), and also active energies (E_a) and pre‐exponential factors (A) of the curing reaction. However, the existence of NS and NC with hydroxyl groups in the structure improves the cure reaction and influence the rate of reaction and therefore kinetics parameters. The E_a of cure reaction of DGEBA/DAAB system showed a decrease when nanoparticles were present and therefore the rate of the reaction was increased. Using the rate constants from the kinetic analysis and transition state theory, thermodynamic parameters such as enthalpy (ΔH^#), entropy (ΔS^#), and Gibbs free energy (ΔG^#) changes were also calculated. The thermodynamic functions were shown to be very sensitive parameters for evaluation of the cure reaction. POLYM. COMPOS., 31:1442–1448, 2010. © 2009 Society of Plastics Engineers     

The effect of CTBN concentrations on the kinetic parameters of decomposition of blends of cardanol‐based epoxidized novolac resin modified with carboxyl‐terminated liquid copolymer

Cardanol‐based novolac resins were separately prepared with different mole ratios of cardanol‐to‐formaldehyde with different acid catalysts. These resins were epoxidized with epichlorohydrin, in basic medium, at 120°C. The resins were, separately, blended with different weight percentages of carboxyl‐terminated butadiene acrylonotrile copolymer and cured with polyamine. Structural changes during blending were studied by FTIR spectroscopic analysis. Coats–Redfern equation was utilized to calculate the kinetic parameters, viz., order of decomposition reaction (n), activation energy (E), pre‐exponential factor (Z), and rate decomposition constant (k), for the decomposition of the samples. It was found that the degradation of the epoxies and their blend samples proceeded in two steps. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Isoconversional and thermal methods of kinetic analysis of 2,4‐dihydroxybenzophenone copolymer resin

A copolymer (2,4‐DHBPOF) synthesized by the condensation of 2,4‐dihydroxybenzophenone and oxamide with formaldehyde in the presence of acid catalyst with varying the molar proportions of the reacting monomer. Composition of the copolymer has been determined by elemental analysis. The copolymer has been characterized by UV–visible, FTIR, and ¹H NMR spectroscopy. The morphology of synthesized copolymer was studied by scanning electron microscopy (SEM). The activation energy (E_a) and thermal stability calculated by using Sharp‐Wentworth, Freeman–Carroll, and Freidman's method. Thermogravimetric analysis (TGA) data were analyzed to estimate the characteristic thermal parameters. Freeman–Carroll and Sharp Wentworth methods have been used to calculate activation energy and thermal stability. The activation energy (E_a) calculated by using the Sharp‐Wentworth has been found to be in good agreement with that calculated by Freeman–Carroll method. Thermodynamic parameters such as free energy change (ΔF), entropy change (ΔS), apparent entropy change (S*), and frequency factor (Z) have also been evaluated based on the data of Freeman–Carroll method. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Kinetics of thermal degradation studies of some new terpolymers derived from 2,4‐dihydroxypropiophenone,oxamide, and formaldehyde

The terpolymers (2,4‐DHPOF) have been synthesized by the condensation of 2,4‐dihydroxypropiophenone with oxamide and formaldehyde in the presence of 2M HCl as catalyst with varying proportions of reactants. Terpolymer composition has been determined on the basis of their elemental analysis. The terpolymer has been characterized by UV‐visible, IR, and ¹H NMR spectra. The thermal decomposition behavior of some new terpolymers was studied using thermogravimetric analysis in air atmosphere at heating rate of 10°C/min. Thermal decomposition curves are discussed with careful attention to minute details. The Freeman–Carroll and Sharp–Wentworth methods have been used to calculate activation energy and thermal stability. Thermal activation energy (E_a) calculated with the help of these methods are in agreement with each other. Thermodynamic parameters such as free energy change (ΔF), entropy change (ΔS), apparent entropy change (S*), and frequency factor (z) are also determined on the basis of the TG curves and by using data of the Freeman–Carroll method. The Freidman method evaluated the variation in the apparent activation energy changes by isoconversional (model‐free) kinetic methods. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(glycerol–sebacate) bioelastomers—kinetics of step‐growth reactions using Fourier Transform (FT)‐Raman spectroscopy

Kinetic studies of the esterification of glycerol (G) and sebacic acid (SA) at three molar ratios (0.6, 0.8, 1.0) and at three temperatures (120, 130, 140°C) to form poly(glycerol–sebacate) were performed and assessed using FT‐Raman spectroscopy. The quantitative changes in the concentrations of carboxylic acid and ester groups within the forming bioelastomer were measured and the chemical rate constants (k) determined from the kinetic scheme were first‐order, with respect to sebacic acid concentration. Increasing the reaction temperature by 20°C is noted to increase the chemical rate constant (k) by a factor of up to 4.5 and the total extent of conversion at early times for the molar ratios investigated. The activation energy (E_a) and the pre‐exponential factor (A₀) for these three stoichiometric ratios were calculated, which varied in accordance with the average functionality of the system. Under isothermal conditions, the chemical rate constant remained unchanged with an increase in the extent of the reaction (α) until a spontaneous transition resulted in the shift in the mechanism from kinetics to diffusion controlled. The Young's moduli of the PGS polymers were found to depend primarily on the average functionality of the system and the curing period. This investigation confirms the reaction mechanism for PGS polymer synthesis and shows the flexibility afforded to PGS properties and reaction times through varying the stoichiometric ratios of glycerol to sebacic acid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

RAFT polymerization of N‐vinyl pyrrolidone using prop‐2‐ynyl morpholine‐4‐carbodithioate as a new chain transfer agent

RAFT polymerization of N‐vinyl pyrrolidone (NVP) has been investigated in the presence of chain transfer agent (CTA), i.e., prop‐2‐ynyl morpholine‐4‐carbodithioate (PMDC). The influence of reaction parameters such as monomer concentration [NVP], molar ratio of [CTA]/[AIBN, i.e., 2,2′‐azobis (2‐methylpropionitrile)] and [NVP]/[CTA], and temperature have been studied with regard to time and conversion limit. This study evidences the parameters leading to an excellent control of molecular weight and molar mass dispersity. NVP has been polymerized by maintaining molar ratio [NVP]: [PMDC]: [AIBN] = 100 : 1 : 0.2. Kinetics of the reaction was strongly influenced by both temperature and [CTA]/[AIBN] ratio and to a lesser extent by monomer concentration. The activation energy (E_a = 31.02 kJ mol^?1) and enthalpy of activation (ΔH^?= 28.29 kJ mol^?1) was in a good agreement to each other. The negative entropy of activation (ΔS^? = ?210.16 J mol^‐1K^‐1) shows that the movement of reactants are highly restricted at transition state during polymerization. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Urethane reaction kinetics of butanediols catalyzed by Zr(acac)4

The urethane reaction of isocyanate was carried out with zirconium acetyl acetonate (Zr(acac)₄) as catalyst. 1,2‐Butanediol and 1,4‐butanediol were used as model compounds to investigate the reaction kinetics. It was shown that hydroxyl groups in 1,2‐butanediol appeared to have different reaction rate when reacting with phenyl isocyanate, which was labeled as k_fast and k_slow. It was very surprising that the reaction rate of 1,4‐butanediol (k_con) was very similar to the value of k_slow at the same temperature although there is only primary hydroxyl group in its molecule. Furthermore, activation energy (E_a), activation enthalpy (ΔH), and activation entropy (ΔS) for the reaction were calculated out, from which some catalytic properties of Zr(acac)₄ were revealed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and reaction kinetics of polypropylene‐graft‐cardanol by reactive extrusion and its compatibilization on polypropylene/polystyrene

Polypropylene‐graft‐cardanol (CAPP) was prepared by reactive extrusion with polypropylene (PP) and natural renewable cardanol, which improved the inherent defects of PP such as its chemical inertness and hydrophobicity. Moreover, the cardanol grafted onto PP resolved the degradation of PP during reactive extrusion and use. The effects of reactive extrusion on the change of the molecular structure of PP, the change in the free‐radical concentration during processing, and the compatibilization of CAPP on the PP/polystyrene (PS) composite materials were examined in this study. The constants of the grafting reaction rate at the beginning of reactive extrusion were also deduced. The results show that cardanol was grafted onto PP, and the p–π conjugate system in cardanol was observed to stabilize free radicals. The grafting reaction rate (R_g) at the initial stage of the grafting reaction process was calculated through the equation R_g = k_g[M·][Cardanol], where k_g is the constant of the apparent grafting reaction rate and [M·] is the concentration of free radicals in the reaction system. k_g first increased with the growth of temperature and then began to decrease when the temperature exceeded the critical temperature of 200°C. The mechanical properties showed almost no change after the samples were aged for 72 h. This was due to CAPP, which changed PP/PS to a ductile material from a brittle one. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39911.     

Synthesis,characterization, and thermal degradation studies of copolymer resin derived from p-cresol,melamine, and formaldehyde

Copolymers (p-CMF) synthesized by the condensation of p-cresol and melamine with formaldehyde in the presence of an acid catalyst and using varied molar proportion of the reacting monomers. Copolymer resin compositions were determined on the basis of their elemental analysis. The number average molecular weight of these copolymers was determined by conductometric titration in nonaqueous media. Solution viscosity measurements in dimethyl sulfoxide (DMSO) were carried out to ascertain the characteristic functions and constants of the copolymer resins. The copolymer resins were further characterized byUV–visible absorption spectra in the nonaqueous medium, Infra-red (IR) spectra, and the nuclear magnetic resonance (NMR) spectra. Thermal studies of the resins were carried out to determine their mode of decomposition, the activation energy (E_a), order of reaction (n), frequency factor (Z), entropy change (ΔS), free energy change (ΔF), and apparent entropy change (S*). Thermal decomposition curves were discussed with careful attention of minute details. The Freeman-Carroll and Sharp-Wentworth methods have been used to calculate thermal activation energy and thermal stability. Thermal activation energy (E_a) calculated with these methods are in agreement with each other. The data from the Freeman-Carroll methods have been used to determine various thermodynamic parameters. The order of thermal stability of copolymers has been determined using TGA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,characterization, and kinetic of thermal degradation of oligo‐2‐[(4‐bromophenylimino)methyl]phenol and oligomer‐metal complexes

Oligo‐2‐[(4‐bromophenylimino)methyl]phenol (OBPIMP) was synthesized from the oxidative polycondensation reaction of 2‐[(4‐bromophenylimino)methyl]phenol (BPIMP) with air and NaOCl oxidants in an aqueous alkaline medium between 50 and 90°C. The yield of OBPIMP was found to be 67 and 88% for air and NaOCl oxidants, respectively. Their structures were confirmed by elemental and spectral such as IR, ultraviolet–visible spectrophotometer (UV–vis), ¹H‐NMR, and ¹³C‐NMR analyses. The characterization was made by TG‐DTA, size exclusion chromatography, and solubility tests. The resulting complexes were characterized by electronic and IR spectral measurements, elemental analysis, AAS, and thermal studies. According to TG analyses, the weight losses of OBPIMP, and oligomer‐metal complexes with Co⁺², Ni⁺², and Cu⁺² ions were found to be 93.04%, 59.80%, 74.23%, and 59.30%, respectively, at 1000°C. Kinetic and thermodynamic parameters of these compounds investigated by Coats‐Redfern, MacCallum‐Tanner, and van Krevelen methods. The values of the apparent activation energies of thermal decomposition (E_a), the reaction order (n), preexponential factor (A), the entropy change (ΔS*), enthalpy change (ΔH*), and free energy change (ΔG*) obtained by earlier‐mentioned methods were all good in agreement with each other. It was found that the thermal stabilities of the complexes follow the order Cu(II) > Co(II) > Ni(II). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Kinetics of alkaline-catalyzed cardanol–formaldehyde reaction. I

The kinetics of reaction between cardanol and formaldehyde when catalyzed by an alkali, sodium hydroxide, has been studied and effects of process parameters, e.g., cardanol formaldehyde molal ratio, catalyst concentration, and temperature have been investigated. The addition reaction has been shown to be a second-order reaction when the concentration of active positions of reactants is used instead of their molar concentrations. Specific reaction rate constants have been determined for various cardanol–formaldehyde molal ratios, catalyst concentrations, and reaction temperatures. The energy of activation, E, is found to be 67.541 MJ/kg-mol (16.132 kcal/mol). The correlation between overall reaction rate constant and the process parameters has also been developed.     

DSC curing study of catalytically synthesized maleic‐acid‐based unsaturated polyesters

Unsaturated polyesters were synthesized based on ethylene glycol and maleic acid as unsaturated dicarboxylic acid, using a variety of saturated acids in the initial acid mixture, without or with different catalysts. The curing of the polyesters produced with styrene was studied using differential scanning calorimetry (DSC) under dynamic‐ and isothermal‐heating conditions. The FTIR spectra of the initial polyesters and cured polyesters were also determined. Curing is not complete at the end of DSC scan and the unreacted bonds were quantitatively determined from the FTIR spectra and by estimation based on literature data. The value of the mean degree of conversion (α) of all double bonds (styrene unit and maleate unit) was approximately α = 0.40. Using an appropriate kinetic model for the curing exotherm of polyesters, the activation energy (E_a), the reaction order (x) and the frequency factor (k_o) were determined. Because the kinetic parameters (ie E_a, k, x) affect the kinetics in various different ways, the curves of degree of conversion versus time at various isothermal conditions are more useful to compare and characterize the curing of polyesters. The kinetic parameters are mainly influenced by the proportion of maleic acid in the polyesterification reaction mixture and secondarily by the residual polyesterification catalyst. The degree of conversion of already crosslinked polyesters is greatly increased by post‐curing them at elevated temperature and for a prolonged time. © 2002 Society of Chemical Industry     

Rice‐husk‐ash‐filled natural rubber. II. Partial replacement of commercial fillers and the effect on the vulcanization process

In a previous investigation, we observed that in the presence of a conventional vulcanization system, the addition of white rice husk ash (WRHA) to natural rubber (NR) compounds increased the rate of crosslinking and lowered the apparent activation energy (E_a) of the vulcanization reaction more strongly than the other fillers used. In this work, commercial fillers, such as precipitated silica (Zeosil‐175) and carbon black (N762), were partially replaced by black rice husk ash and WRHA. Cure studies were carried out on a TI‐100 curometer at 150, 160, 170, and 180°C, and the overall rates and the E_a's for the vulcanization process were calculated for each compound, with the assumption that vulcanization followed first‐order kinetics. Again, WRHA showed some catalytic effect on the NR vulcanization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1405–1413, 2003     

Synthesis and characterization of poly(L‐lactide‐co‐ϵ‐caprolactone)‐b‐poly(L‐lactide) biodegradable diblock copolyesters: Effect of the block lengths on their thermal properties

Poly(L ‐lactide‐co‐ε‐caprolactone)‐b‐poly(L ‐lactide) [P(LL‐co‐CL)‐b‐PLL] diblock copolyesters were synthesized in a two‐step process with 1‐dodecanol (DDC) and stannous octoate as the initiating system. In the first‐step reaction, a 50:50 mol % amorphous poly(L ‐lactide‐co‐ε‐caprolactone) [P(LL‐co‐CL)] copolyester was synthesized via the bulk copolymerization of L ‐lactide and ε‐caprolactone, which was followed by the polymerization of the PLL crystalline block at the end chain in the second‐step reaction. The yielded copolyesters were characterized with dilute‐solution viscometry, gel permeation chromatography, ¹H‐ and ¹³C‐NMR, and differential scanning calorimetry methods. The molecular weights of the P(LL‐co‐CL) copolyesters from the first‐step reaction were controlled by the DDC concentrations, whereas in the second‐step reaction, the molecular weights of the P(LL‐co‐CL)‐b‐PLL diblock copolyesters depended on the starting P(LL‐co‐CL) copolyester molecular weights and L ‐lactide/prepolymer molar ratios. The starting P(LL‐co‐CL) copolyester molecular weights and PLL block lengths seemed to be the main factors affecting specific thermal properties, including the melting temperature (T_m), heat of melting (ΔH_m), crystallizing temperature (T_c), and heat of crystallizing (ΔH_c), of the final P(LL‐co‐CL)‐b‐PLL diblock copolyester products. T_m, ΔH_m, T_c, and ΔH_c increased when the PLL block lengths increased. However, these thermal properties of the diblock copolyesters also decreased when the P(LL‐co‐CL) block lengths increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation of cardanol–formaldehyde resins from cashew nut shell liquid for the reinforcement of natural rubber

Natural rubber was reinforced with a high loading of a cardanol–formaldehyde resin prepared from cashew nut shell liquid. Cardanol–formaldehyde resins, both resoles and novolaks, were synthesized from cardanol, which was extracted from cashew nut shells. This was done by the condensation polymerization of cardanol and formaldehyde in the presence of base and acid catalysts. The cardanol–formaldehyde resole with the highest yield (ca. 75%) was prepared with a formaldehyde/cardanol molar ratio of 2.0 at pH 8.0 and 90°C for 8 h. The cardanol–formaldehyde novolak with the highest yield (ca. 80%) was prepared with a formaldehyde/cardanol molar ratio of 0.8 at pH 2.2 and 100°C for 7 h. Fourier transform infrared and ¹³C‐NMR were employed to characterize the chemical structures of the obtained cardanol–formaldehyde resins. The resins were compatible with natural rubber in various formulations. The cured behaviors of natural rubber blended with the cardanol–formaldehyde resole and novolak resins were investigated. The cured behaviors of cardanol–formaldehyde resole and cardanol–formaldehyde novolak samples were different, reflecting differences in their chemical reactivities. Furthermore, the incorporation of cardanol–formaldehyde resins into natural rubber provided significant improvements in mechanical properties such as the hardness, tensile strength, modulus at 100 and 300% elongation, and abrasion resistance. However, the elongation at break and compression set of the blends decreased as expected. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1997–2002, 2007     

Direct functionalization with 3,5‐substituted benzoic acids of multiwalled carbon nanotube/epoxy composites

Directly functionalized multiwalled carbon nanotubes (MWCNTs) with benzene‐1,3,5‐tricarboxylic acid (BTC) and 3,5‐diaminobenzoic acid (DAB) were successfully accomplished with less structural damage as confirmed by XPS and FT‐Raman results. Their dispersibility and thermal stability were achieved after the functionalization. The functional groups on MWCNT surfaces can accelerate the curing reaction of epoxy composites remarkable inducing rather low exothermic peak temperature (T_p) and exothermic heat of reaction (ΔH). The values of activation energy (E_a) obtained from Kissinger and Ozawa methods obviously decreased with the introduction of MWCNTs, especially DAB‐MWCNTs. The dynamic mechanical properties notably enhanced with the incorporation of unmodified and functionalized MWCNTs. The crosslink density (ρ) increased and free volume fraction (f_g) decreased, resulting in dramatic increase of glass transition temperatures (T_g) and decrease of coefficient of thermal expansion. Additionally, epoxy composites exhibited low dielectric constant close to that of neat epoxy resin. From these remarkable properties, MWCNT/epoxy composites can be considered as a good candidate for high performance insulation materials. POLYM. ENG. SCI., 53:2194–2204, 2013. © 2013 Society of Plastics Engineers     

Kinetics of alkaline-catalyzed cardanol–formaldehyde reaction. II. Mechanism of the reaction

The mechanism of the reaction between cardanol and formaldehyde when catalyzed by an alkali, sodium hydroxide, has been investigated. It was observed that only three individual rate constants, k₁₁, k₁₂, and k₁₃, out of 12 appearing in the mechanism could be quantitatively estimated due to poor separation of the intermediates. The equation for the rate of overall chemical reaction has been developed and found to agree well with the experimental data.     

Synthesis,characterization, conductivity,band gap,and kinetic of thermal degradation of poly‐4‐[(2‐mercaptophenyl) imino methyl] phenol

The oxidative polycondensation reaction conditions of 4‐[(2‐mercaptophenyl) imino methyl] phenol (2‐MPIMP) were studied in an aqueous acidic medium between 40 and 90°C by using oxidants such as air, H₂O₂, and NaOCl. The structures of the synthesized monomer and polymer were confirmed by FTIR, ¹H NMR, ¹³C NMR, and elemental analysis. The characterization was made by TGA‐DTA, size exclusion chromatography (SEC) and solubility tests. At the optimum reaction conditions, the yield of poly‐4‐[(2‐mercaptophenyl) imino methyl]phenol (P‐2‐MPIMP) was found to be 92% for NaOCl oxidant, 84% for H₂O₂ oxidant 54% for air oxidant. According to the SEC analysis, the number‐average molecular weight (M_n), weight‐average molecular weight (M_w), and polydispersity index values of P‐2‐MPIMP were found to be 1700 g mol^?1, 1900 g mol^?1, and 1.118, using H₂O₂; 3100 g mol^?1, 3400 g mol^?1, and 1.097, using air; and 6750 g mol^?1, 6900 g mol^?1, and 1.022, using NaOCl, respectively. According to TG analysis, the weight losses of 2‐MPIMP and P‐2‐MPIMP were found to be 95.93% and 76.41% at 1000°C, respectively. P‐2‐MPIMP showed higher stability against thermal decomposition. Also, electrical conductivity of the P‐2‐MPIMP was measured, showing that the polymer is a typical semiconductor. The highest occupied molecular orbital, the lowest unoccupied molecular orbital, and the electrochemical energy gaps (E′_g) of 2‐MPIMP and P‐2‐MPIMP were found to be ?6.13, ?6.09; ?2.65, ?2.67; and 3.48, 3.42 eV, respectively. Kinetic and thermodynamic parameters of these compounds investigated by MacCallum‐Tanner and van Krevelen methods. The values of the apparent activation energies of thermal decomposition (E_a), the reaction order (n), pre‐exponential factor (A), the entropy change (ΔS*), enthalpy change (ΔH*), and free energy change (ΔG*) were calculated from the TGA curves of compounds. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Octa(aminophenyl) polyhedral oligomeric silsesquioxane/boron‐containing phenol–formaldehyde resin nanocomposites: Synthesis,cured, and thermal properties

Octa(aminophenyl) polyhedral oligomeric silsesquioxane (OAP‐POSS) and boron‐containing phenol‐formaldehyde resin (BPFR) were synthesized, respectively. The BPFR nanocomposites with different OAP‐POSS content (wt%) were prepared, and their properties were characterized. The results show that the thermal degradation process of this nanocomposites can be divided into three stages, and they are all following the first order mechanism. The residual ratio and thermal degradation activation energy E_a of 9 wt% OAP‐POSS/BPFR nanocomposites are both better than others and the E_a increase gradually in three stages, which is 93.3, 134.0, and 181.9 kJ mol⁻¹, respectively. Its residual ratio at 900°C is 36.48%. The mechanical loss peak temperature T_p is 228°C for 12 wt% OAP‐POSSS/BPFR nanocomposites, which is higher 48°C than pure BPFR. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Interfacial encapsulation of bio‐based benzoxazines in epoxy shells for temperature triggered healing

Successful application of interfacial engineering for the preparation of cross‐linked epoxy microspheres containing thermally polymerizable cardanol‐based benzoxazine (Bz‐C) monomer in the core is demonstrated. Bz‐C is facilely synthesized by Mannich type condensation of cardanol (a by‐product of cashew nut industry) and aniline with formaldehyde under solventless conditions. The encapsulation process relies on the preferential reaction of polydimethylsiloxane immiscible epoxy resin and amine‐based hardener to form a cross‐linked spherical shell at the interface. The microcapsule dimensions and core content could be tailored by modulating the operating parameters, particularly stirring speed and Bz‐C: epoxy ratio. Spherical microcapsules with a core content of ～37% were obtained when the reaction was carried out at 600 rpm, while maintaining the reaction medium at 70°C with Bz‐C: epoxy ratio of 2.3 : 1. The simplicity and versatility of the present methodology are the forte of this technique, which widens the scope for large‐scale application of benzoxazines in the field of temperature triggered healing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42832.