Nonisothermal cure of bisphenol epoxy resin with a nonlinear aliphatic polyamine hardener

The amino terminated polypropylenimine dendrimer (DAB‐dendri‐(NH₂)₄) was employed as a new nonlinear aliphatic curing agent for diglycidyl ether of bisphenol A (DGEBA). Nonisothermal curing reaction kinetics of DGEBA/DAB was investigated with a differential scanning calorimeter (DSC). The apparent reaction activation energy E_a is about 56.7 kJ/mol determined using the Kissinger equation, and a two‐parameter (m, n) autocatalytic model ([icirc]Sesták–Berggren equation) was confirmed to be able to well simulate the reaction kinetics in the light of the Málek method. In addition, the relation between reaction activation energy E_a and curing degree α was obtained by applying model‐free isoconversional analysis with the Kissinger‐Akahira‐Sunose (KAS) method. As α increases, E_a reduced quickly from >80 kJ/mol to ≈60 kJ/mol up to a ≈ 15%, then decreased slowly to 55 kJ/mol till a ～ 75%, and finally dropped to 44 kJ/mol at full conversion. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effects of microwave heating on the kinetics of isothermal dehydration of equilibrium swollen poly(acrylic‐co‐methacrylic acid) hydrogel

The isothermal dehydration of poly(acrylic‐co‐methacrylic acid) (PAM) hydrogel under microwave heating (MWH) was investigated. The isothermal kinetics curves of the PAM hydrogel dehydration at temperature range from 293 K to 333 K were recorded. Based on the differential isoconversion method it was concluded that the microwave dehydration of poly(acrylic‐co‐methacrylic acid) hydrogel is an elementary kinetics process. Applying the model‐fitting method it was established that the kinetics of microwave isothermal hydrogel dehydration can be described by the kinetics model of the phase‐boundary controlled process (contracting area). The values of the kinetics parameters (activation energy (E_a) and preexponential factor (lnA)) of the dehydration process under microwave heating are lower than the values for conventional heating (CH). The established influence of MWH on the kinetics of hydrogel dehydration is explained with a specific activation mechanism of water molecules for dehydration and with the increase in the value of the energy of the ground level of the resonant oscillator of water molecule (v = 837 cm^?1) due to the absorption of microwave energy. POLYM. ENG. SCI., 56:87–96, 2016. © 2015 Society of Plastics Engineers     

Influence of microwave heating on the kinetic of acrylic acid polymerization and crosslinking

Kinetics of isothermal formation of poly (acrylic acid) (PAA) hydrogels through polymerization of acrylic acid and crosslinking of the PAA formed in a conventionally heated reaction system and in a microwave heated reaction system were investigated. It was found that in the microwave heated system the reaction rate constant of PAA hydrogel formation significantly increased (from 32 to 43 times) when compared with the conventionally heated system. The isothermal kinetics of the PAA hydrogel formation during the microwave process could be described by the so‐called first‐order chemical reaction kinetics model. In contrast, the so‐called second‐order chemical reaction rate model could best describe the isothermal kinetics of the PAA hydrogel formation during the conventionally heated process. Also, in the microwave heated system, the reaction kinetics of the PAA hydrogel formation and its kinetic parameters changed, that is, the activation energy (E_a) decreased by about 19% and the pre‐exponential factor (lnA) decreased by 2.2 times. The decrease in activation energy, change in entropy of activation energy, and decrease in the pre‐exponential value of PAA hydrogel formation under microwave heating are caused with increased energy of the reactive species when compared with their energy in thermal activation. Increased energy of the reactive species is a consequence of rapid transfer and absorption of the energy of microwave field to the existing reactive species. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Kinetics of Isothermal Ethanol Adsorption onto a Carbon Molecular Sieve under Conventional and Microwave Heating

The isothermal kinetics of ethanol adsorption from aqueous solution onto a zeolite type carbon molecular sieve (CMS‐3A) under conventional heating (CH) and microwave heating (MWH) was investigated. The adsorption kinetics is described by the model of a phase‐boundary controlled reaction for both heating modes. The activation energy (E_a) for the adsorption process under MWH is lower than under CH while the preexponential factor (lnA) is higher. Ethanol adsorption is a kinetically complex process whose complexity changes with the mode of heating. The established decrease in E_a and increase in lnA under MWH compared to CH is explained with the increase in the ground vibrational level of the – OH twisting vibrations in the ethanol molecule and with the decrease in its anharmonicity factor which is caused by the selective resonant transfer of energy from CMS‐3A to the OH oscillators.     

Nonisothermal Co-Polymerizing Behavior and Thermal Properties of Methylacyloxylpropyl-POSS with Styrene

The methylacryloylpropyl-polyhedral oligomeric silsesquioxanes (MAP-POSS) was introduced into the PSt by copolymerization. The copolymerizing kinetics was investigated by non-isothermal DSC. The mechanical loss peak temperature T _p and thermal properties were determined by DMA and TGA. The results show that the compatibility of MAP-POSS with styrene is very well and can copolymerization. The relationship of polymerization E _a and conversion α be obtained. The copolymerization reactions can be described by the autocatalytic ?esták-Berggren (S-B) equation. The T _p was increased about 13°C than pure PSt, and up to a maximum of 110.8°C when the MAP-POSS contents is 10 wt%.     

Tl(III) initiated polymerization of methyl methacrylate in micellar phase

The polymerization kinetics of methyl methacrylate (MMA) was studied, using Tl(III)‐cyclohexanone (CH) redox system as initiator, in the presence of emulsifier [i.e., sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB), and thallium triacetate (TX‐100)] over a temperature range of 25–45°C. The effect of various concentrations of MMA, Tl(III), cyclohexanone, H⁺, and varying ionic strengths on the rate of polymerization, rate of Tl(III) consumption (?R_Tl), and the percentage of monomer conversion were examined in the presence of 0.015M SDS. The kinetic results of polymerization in the absence and presence of 0.015M SDS were compared in terms of overall activation energy (E_a) for the process. The viscosity‐average molecular weight (M_V) of the polymers, obtained in the presence of varying concentrations of anionic surfactant (SDS), was also determined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2480–2485, 2004     

Fabrication and apparent kinetic study of poly(methyl methacrylate)/poly(octyl acrylate) and poly(octyl acrylate)/poly(methyl methacrylate) latex interpenetrating polymer networks

Two latex interpenetrating polymer networks (LIPNs) were synthesized with methyl methacrylate (MMA) and octyl acrylate (OA) as monomers, respectively. The apparent kinetics of polymerization for the LIPNs was studied. This demonstrates that network II does not have a nucleus formation stage. The monomers of network II were diffused into the latex particles of network I and then formed network II by in situ polymerization. It indicates that the polymerization of network I obeys the classical kinetic rules of emulsion polymerization. But the polymerization of network II only appears a constant‐rate stage and a decreasing‐rate stage. The apparent activation energies (E_a) of network I and network II of PMMA/POA were calculated according to the Arrhenius equation. The E_a values of POA as network I (62 kJ/mol) is similar to that of POA as network II PMMA/POA (60 kJ/mol). However, the E_a value of PMMA as network II POA/PMMA (105kJ/mol) is higher than that of PMMA as network I (61 kJ/mol). Results show that the E_a value of the network II polymerization is related to the properties of its seed latex. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Photochemical-induced polymerization kinetics of styrene and methyl methacrylate by initiation of binary system composed of polyethylene oxide with aniline end group and benzophenone

The kinetics of photochemical polymerization of styrene (St) and methyl methacrylate (MMA) using a binary initiation system composed of poly(ethylene oxide) with an aniline end group (PEO_a) and benzophenone (BP) was investigated by a modified dilatometer. The effect of the concentration of the monomer, BP and PEO_a, and of the molecular weight of PEO_a on the polymerization rate (R_p) and conversion of monomers is discussed in detail. The formulas of R_p ∝︁ [PEO_a]^0.38 [St]^0.33 [BP]^0.56 and R_p ∝︁ [PEO_a]^0.36 [MMA]^0.30 [BP]^0.54 using benzene as a solvent are derived when the molecular weight of PEO is 11,000 (PEO_a — 11,000). Compared with the small aminophenol (AP), there existed a critical PEO_a concentration to affect the R_p and conversion of the monomers and the critical concentration is strongly dependent on the polarity of the solvents and molecular weight of PEO_a. It is confirmed that in the same conditions the solution polymerization behavior of St and MMA initiated by the imino radical of PEO would not be affected by the properties of the second block although PMMA is miscible and PS is immiscible with PEO_a in the bulk. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2095–2103, 1997     

Comparative study on isothermal kinetics of fullerol formation under conventional and microwave heating

The kinetic of fullerol formation in the presence of cetyl trimethyl ammonium bromide (CTAB) as a phase transfer catalyst both under conventional and microwave heating conditions was investigated. It was found that the activation energy (E_a) for the investigated processes under microwave heating was two to four times lower than for the same, conventionally heated process. Also, the pre-exponential factor (ln A) was 436–4200 times lower for the microwave heating process. The differences in the kinetic parameters (activation energy and pre-exponential factor) of the process under microwaves can be explained with the specific (non-thermal) activation of centres of the newly formed phase due to the electromagnetic energy absorption.     

Optical Properties of Gamma-Irradiated ST/MMA Copolymer

Copolymer films, with various concentrations of styrene (ST) and methyl-methacrylate (MMA), were prepared by thermal polymerization. The films were exposed to different doses of gamma rays up to 10 Mrad. The optical absorption α and the optical parameters, including the energy band gap E _g and band tail width E _w , were estimated for the films before and after irradiation by gamma rays. Furthermore, the effect of UV radiation on un-irradiated films was investigated. The specular reflection of PS, PMMA, and copolymer has been measured. The refractive index and Cauchy's constants were evaluated for the films before and after irradiation by gamma rays. The structure–property behavior of the films was scrutinized by DSC and FT-IR.     

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     

Effect of solvent proton affinity on the kinetics of michael addition polymerization of n,n′‐bismaleimide‐4,4′‐diphenylmethane with barbituric acid

The effect of solvent proton affinity on the kinetics of the Michael addition polymerizations of N,N′‐bismaleimide‐4,4′‐diphenylmethane (BMI) and barbituric acid (BTA) in different solvents [N‐methyl‐2‐pyrrolidone (NMP), N,N′‐dimethylacetamide (DMAC), and N,N′‐dimethylformamide (DMF)] were investigated. This was achieved by the complete suppression of the competitive free radical polymerization via the addition of a sufficient amount of hydroquinone (HQ). A mechanistic model was developed to adequately predict the polymerization kinetics before a critical conversion, at which point the diffusion‐controlled polymerization become the predominant factor during the latter stage of polymerization, was achieved. The activation energy (E_a) of the Michael addition polymerization of BMI with BTA in the presence of HQ in increasing order was: NMP < DMAC < DMF, which was correlated quite well with the solvent proton affinity (NMP > DMAC > DMF). By contrast, the frequency factor (A) in increasing order is: NMP < DMAC < DMF. As a result of the compensation effect between E_a and A, at constant temperature, the Michael addition rate constant decreased with increasing solvent proton affinity. POLYM. ENG. SCI., 54:559–568, 2014. © 2013 Society of Plastics Engineers     

Novel approach in investigation of the poly(acrylic acid) hydrogel swelling kinetics in water

The swelling kinetics curves of structurally defined poly(acrylic acid) hydrogel in bidistilled water at temperatures: 25, 30, 35, 40, and 45°C were determined. The possibility of kinetically explaining the isothermal swelling process by applying the following models: reaction controlled by diffusion, first order chemical reaction kinetics, and second order chemical reaction kinetics, was investigated. It was found that kinetically explaining the swelling process using these methods was limited to only certain parts of the process. The swelling process in bidistilled water was described in full range assuming that the hydrogel's swelling rate was a kinetically controlled reaction by the rate of the movement of reactive interface of hydrogel. Based on that model, the kinetic parameters, activation energy (E_a) and preexponential factor (A), of the swelling process were determined to be E_a = 35 kJ/mol and lnA = 8.6. A possible mechanism of the investigated swelling process was discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal decomposition of 3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane in solution and its use in methyl methacrylate polymerization

The kinetics of the thermal decomposition reaction of diethylketone triperoxide (3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane, DEKTP) in ethylbenzene solution were studied in the temperature range of 120.0–150.0 °C and at an initial concentration range of 0.01–0.10 M. This peroxide was used as a new initiator in methyl methacrylate (MMA) polymerization process at high temperatures (110.0–140.0 °C) in ethylbenzene solution. The effects of initiator concentration and reaction temperature on the polymerization rate were investigated in detail. Thus, activation parameters of the solution polymerization process (ΔE _d* = 83.3 kJ mol⁻¹ and ΔE _p* − ΔE _t*/2 = 54.0 kJ mol⁻¹) will be obtained. DEKTP can effectively act as initiator in MMA polymerization and its performance is similar to that presented by a multifunctional initiator resulting in high-molecular weight polymethylmethacrylate with a high reaction rate.     

Preparation of soap‐free cationic emulsion using polymerizable surfactant

A kind of polymerizable surfactant, methacryloyloxyethylhexadecyldimethylammonium bromide (DMHB) was used to synthesis soap‐free cationic emulsion with styrene (St), methyl methacrylate (MMA), and methacryloyloxyethyltrimethylammonium chloride (MATMAC) by emulsion polymerization using 2,2′‐azobis(isobutylamidine hydrochloride) (AIBA) as a cationic initiator. The effects of polymerizable surfactant concentration, initiator concentration, and reaction temperature on the conversion of monomer were investigated. The results indicated that the rate of polymerization could be expressed as R_p = k_p[AIBA]^0.42[DMHB]^0.45 and the apparent activation energy (E_a) was 83.42 kJ/mol. The particle size, ζ potential, and apparent charge density of cationic latices were also measured. The average diameter of copolymer particles decreased with increasing DMHB, MATMAC, and AIBA content; the charge properties of the particles were decided by the DMHB, MATMAC, and AIBA content. The polymerization mechanism is discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1111–1116, 2006     

Synthesis, characterization polymerization and antibacterial properties of novel thiophene substituted acrylamide

Ethyl 2-acrylamido-4,5,6,7-tetrahydrobenzo [b] thiophene-3-carboxylate (ETTCA) has been synthesized and its structure has been elucidated by elemental analysis and spectral tools. Free radical polymerization of (ETTCA) has been conducted in several solvents using azobisisobutyronitrile (AIBN) as an initiator. The kinetic parameters of polymerization of the ETTCA were investigated, and it was found that the polymerization reaction follows the conventional free radical scheme. The overall activation energy of polymerization ΔE was determined (ΔE = 45.11 kJ mol⁻¹). The copolymerization of ETTCA with three conventional monomers was carried out in dioxane at 65 °C. The monomer reactivity ratios for the copolymerization of ETTCA with methyl methacrylate (MMA), vinyl acetate (VA) and vinyl ether (VE) were calculated. Thermal stability of the ETTCA polymer and its copolymers were investigated by thermogravimetric analysis. It has been found that the prepared polymer (PETTCA) and its copolymers with VA have moderate biological activity and highly dependent on the copolymer composition.     

Nonisothermal cure kinetics and diffusion effect of liquid-crystalline epoxy sulfonyl bis(1,4-phenylene)bis[4-(2,3-epoxypropyloxy)benzoate] resin with aromatic diamine

The curing kinetics of the liquid-crystalline epoxy resin sulfonyl bis(1,4-phenylene)bis[4-(2,3-epoxypropyloxy)benzoate] with 4,4′-diaminodiphenylsulfone was investigated by nonisothermal differential scanning calorimetry. The relationship between the apparent activation energy (E_a) and the conversion was determined, and the effects of the molecular structure and the order of liquid crystallinity on E_a are discussed in detail. Some parameters were evaluated with the autocatalytic kinetic model of the Šesták–Berggren (S–B) equation. The results show that there were some deviations of these simulation curves from the experimental curves at high heating rates and in the late stage of the curing reaction. The diffusion effect in the nonisothermal curing reaction is discussed, and a diffusion factor was proposed and introduced into the S–B equation. Then, a modified S–B equation was created, as follows: , where α is the conversion, t is the time, m and n are reaction orders, K is rate constant, C is the diffusion coefficient, and α_c is the critical conversion. The theoretical simulation curves agreed very well with the experimental data as determined with the modified S–B equation, which may be more useful for describing and predicting the nonisothermal curing reaction kinetics of epoxy resin. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Kinetic study of atom transfer radical polymerization of methyl methacrylate in ionic liquids

The kinetics of methyl methacrylate (MMA) homopolymerization performed by atom transfer radical polymerization (ATRP) is investigated in detail using ethyl‐2‐bromopropionate (EPN‐Br) as initiator, CuBr as catalyst, and pentamethyldiethylenetriamine (PMDETA) as ligand in ionic liquids (ILs) and acetonitrile. ILs in this research covered two different substitutional imidazolium cations and anions including halogen and halogen‐free ones. The typical cations include 1‐butyl‐3‐methylimidazolium, 1‐ethyl‐3‐methylimidazolium and the typical anions include bromide, tetrafluoroborate. The effects of solvents, temperature, and reaction ingredients ratios on the polymerization kinetics are all investigated in this article and the apparent energy of activation (ΔE) calculated for the ATRP of MMA in 1‐butyl‐3‐methyl‐imidazolium tetrafluoroborate is 6.95 KJ/mol. The number‐average molecular weights (M_n) increase linearly with conversion but are much higher than the theoretical values. It is probably due to the low concentration of deactivator at the early stage of polymerization and the lower bond energy of C‐Br in PMMA‐Br than that in EPN‐Br. Moreover, the catalyst is easily separated from the polymer and the regenerated catalyst is reused for more than three times. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of primary structural parameters of poly(methacrylic acid) xerogels on the kinetics of swelling

Xerogels of poly(methacrylic acid) (MAXG) with different primary structural parameters (PSP) [number average molar mass between the network crosslinks (M_c), the crosslink degree (ρ_c), and the distance between the macromolecular chains (d)] are successfully synthesized by crosslinking free‐radical polymerization. The isothermal swelling curves of synthesized MAXG are measured in distilled water in the temperature range of 25–40°C. The swelling conversion curves of all the MAXG may be described with kinetics model of phase boundary controlled reaction, i.e., contracting area (R2). The values of swelling kinetics parameters (E_a and lnA) linearly increase with the increase in M_c. This work presented a novel and quantum model of the mechanism of xerogel's swelling activation process based on resonant coupling of vibration oscillation of water molecules and vibration modes of xerogel. A quantum nature of E_a of swelling process is proved and explained the effects of PSP on the values of swelling kinetics parameters. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013