Properties of bismaleimide resin modified with polyrotaxane as a stress relaxation material

In this study, 4,4′‐diphenylmethane bismaleimide (BMI)/2,2′‐diallylbisphenol A (DABPA) resin was modified with polyrotaxane (PR) as a stress relaxation material. Based on a dynamic mechanical analysis and various properties of the cured resin, the influence of the motion of PR on the cured properties of BMI/DABPA/PR alloy is discussed. The cyclic molecule α‐cyclodextrin (α‐CD) that is threaded onto the PR axis contains a methacryl group in its side chain that reacts with the allyl group of BMI/DABPA resin. The methacryl group of PR reacted with the allyl group of BMI/DABPA matrix resin to form a transparent and dense network structure, so that the glass transition temperature was increased with increasing PR concentration. In addition, the toughness, impact resistance and adhesiveness of BMI/DABPA resin were improved by modification with PR. These results indicate that the poly(ethylene glycol) chain, which is the axial polymer of the PR, moves in the space formed by the cavities of the threaded α‐CD and the surrounding BMI/DABPA resin matrix in the glassy state, thereby relaxing the internal stress applied to BMI/DABPA/PR resin. The range of applications of BMI/DABPA resin modified with PR may expand into fields requiring high heat resistance in addition to excellent toughness and adhesiveness. © 2018 Society of Chemical Industry     

Electron‐beam curing of bismaleimide‐reactive diluent resins

Electron‐beam (E‐beam) curing of 4,4′‐bismaleimidodiphenylmethane (BMPM)/BMI‐1,3‐tolyl/o,o′‐diallylbisphenol A (DABPA)–based bismaleimide (BMI) systems and their mixing with various reactive diluents, such as N‐vinylpyrrolidone (NVP) and styrene, were investigated to elucidate how temperature, electron‐beam dosage, and diluent concentration affect the cure extent. The effect of free‐radical initiator on the cure reactions was also studied. It was found that low‐intensity E‐beam exposures cannot cause the polymerization of BMI. High‐intensity E‐beam exposures give high reaction conversion attributed to a high temperature increase, which induced thermal curing. It was shown that the dilution and activation of NVP in BMI cause a more complete BMI cure reaction under E‐beam radiation. BMI/NVP can be initiated easily by low‐intensity E‐beam without thermal curing. FTIR studies indicate that about 70% of the reaction is complete for BMI/NVP with 200 kGy dosage exposure at 10 kGy per pass. The sample temperature only reaches about 75°C. The free‐radical initiator, dicumyl peroxide, can accelerate the reaction rate at the beginning of E‐beam exposure, but does not affect the final reaction conversion. The increase of the concentration of NVP in the BMI/NVP systems increases the reactive conversions almost linearly. © 2004 Wiley Periodicals Inc. J Appl Polym Sci 94: 2407‐2416, 2004     

Cure kinetic study of carbon nanofibers/epoxy composites by isothermal DSC

An investigation was carried out into the cure kinetics of carbon nanofibers (CNF)/epoxy composites, composed of tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM) resin and 4,4′‐diaminodiphenylsulfone (DDS) as a curing agent. The experimental data for both neat system and CNF/epoxy composites revealed an autocatalytic behavior. Analysis of DSC data indicated that the presence of carbon nanofibers had only a negligible effect on the cure kinetics of the epoxy. Kinetic analysis was performed using the phenomenological model of Kamal and two diffusion factors were introduced to describe the cure reaction in the latter stage. Activation energies and kinetic parameters were determined by fitting experimental data. Comparison between the two diffusion factors was performed, showing that the modified factor was successfully applied to the experimental data over the whole curing temperature range. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 329–335, 2005     

Fluorinated bismaleimide resin with good processability,high toughness,and outstanding dielectric properties

In this study, novel fluorinated bismaleimide (BMI) resins were prepared by the copolymerization of 2,2′‐bis[4‐(4‐maleimidephenoxy)phenyl]hexafluoropropane (6FBMP) and diallyl hexafluorobisphenol A (6FDABPA) to enhance their dielectric properties. The dielectric properties of the resins were investigated in the frequency range 7–18 GHz through a cavity method. Through the incorporation of a hexafluoroisopropyl group with the polymer chain, the dielectric constant (ε) was effectively decreased because of the small dipole and the low polarizability of the carbon‐fluorine (C? F) bonds. The 6FBMP/6FDABPA resin possessed excellent dielectric properties, with ε being 2.88 and the dielectric loss being 0.009 at 10 GHz and 25°C. In comparison with the 4,4′‐bismaleimidodiphenylmethane (BDM)/2,2′‐diallyl bisphenol A (DABPA) resin, the glass‐transition temperature (T_g) of 6FBMP/6FDABPA decreased. The flexible ether group in the long chain of 6FBMP was considered to disrupt chain packing and cause a decreased crosslinking density and a lower T_g. 6FBMP/6FDABPA showed a similar thermal decomposition temperature and good thermal properties like the BDM/DABPA resin, whereas the impact strength of the 6FBMP/6FDABPA resin was almost 1.6 times higher than that of the BDM/DABPA resin. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42791.     

Cure kinetics of T700/BMI prepreg used for advanced thermoset composite

A new isothermally based, cure kinetic model for the prepreg was presented using an industrially supplied prepreg rather than pure resin. The matrix resin was bismaleimide (BMI) resins, and the reinforcement was carbon fiber T700–12S. The BMI prepreg was measured from 170 to 220°C by isothermal DSC. The isothermal cure reaction heat increases with the increment of cure temperature. The DSC data were analyzed by the proposed nth‐order reaction model. An increase in reaction rate was observed at higher temperature in both neat and prepreg. After reaching the peak value, the reaction rate dropped off faster in prepreg, resulting in a lower average value of the ultimate heat of reaction. It was suggested the presence of carbon fiber had an effect on the cure kinetics as a heat sink. The carbon fibers imposed restrictions on the molecular mobility of the reactive species and did not change the cure mechanism. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2238–2241, 2005     

Cure kinetics,phase behaviors,and fracture properties of bismaleimide resin toughened by poly(phthalazinone ether ketone)

Poly(phthalazinone ether ketone)s (PPEK) were used to toughen bismaleimide (BMI) resin composed of 4,4′‐bismaleimidodiphenyl methane (BMDM) and O,O′‐diallyl bisphenyl A (DABPA). Dynamic differential scanning calorimetry (DSC) of the blends was carried out for kinetic analysis of the curing reaction. The reaction activation energy indicated that the reaction mechanism remained the same even after the incorporation of PPEK. The reaction‐induced phase separation process in BMI/PPEK blends was investigated by optical microscopy (OM). The primary phase structure of the blends was fixed at the early stage of phase separation, and a secondary phase separation was observed as a result of the high viscosity of the blends. Scanning electron microscope (SEM) graphs showed that the morphology of the cured resin changed from a dispersed structure to a phase‐inverted structure with the increase of PPEK content. Compared with the neat resin, the fracture toughness of the modified resin exhibits a moderate increase when PPEK was incorporated. Several toughening mechanisms, such as local plastic deformation, crack deflection, and branches, presumably took part in improving the toughness of BMI/PPEK blends on the basis of the morphology. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Cure kinetics of epoxy/anhydride nanocomposite systems with added reactive flame retardants

Montmorillonite nanocomposite systems obtained from epoxy cured using anhydride and the addition of a reacting flame retardant are studied in this paper. In particular, a thermokinetic analysis of the behavior of five different compounds was performed, using a differential scanning calorimeter. The isothermal tests showed double reaction peaks, due to the cure reactions of DGEBA/acid anhydride systems. The comparisons between dynamic thermograms (and between isothermal ones, too) for the different mixtures also showed that the addition of other active substances (such as a nanofiller or a flame retardant additive) does not change the mechanism of crosslinking from a qualitative point of view, but both the nanoreinforcement and the flame retardant seemed to exert an evident catalytic action on the cure reactions. A model describing the cure behavior of the aforementioned materials is proposed in this work. This model takes into account the fact that the reaction mechanism of each analyzed system is composed of a couple of parallel phenomena: the fast opening of anhydride ring (corresponding to a first exothermic peak and characterized by “n‐th order” kinetics) and resin networking (corresponding to a second exothermic peak and characterized by an “auto‐catalytic with zero initial velocity” behavior). The verification of the proposed model was performed by means of a comparison between experimental data (normalized curves derived from DSC thermograms) and theoretical data (derived from a numerical integration—using the second order Runge–Kutta method—of the model‐representative equation) and provided very good results. This allows one to apply such a model to any engineering process problem concerning the cure of DGEBA/acid anhydride/phyllosilicate nanocomposite systems. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1676–1689, 2004     

Curing kinetics and thermal property characterization of an o‐cresol formaldehyde epoxy resin and 4,4′‐diaminodiphenyl ether system

The kinetics of the curing reaction for a system of o‐cresol formaldehyde epoxy resin (o‐CFER) with 4,4′‐diaminodiphenyl ether (DDE) as a curing agent were investigated with differential scanning calorimetry (DSC). An analysis of the DSC data indicated that an autocatalytic behavior appeared in the first stages of the cure for the system, and this could be well described by the model proposed by Kamal, which includes two rate constants and two reaction orders (m and n). The overall reaction order (m + n) was 2.7–3.1, and the activation energies were 66.79 and 49.29 kJ mol^?1, respectively. In the later stages, a crosslinked network was formed, and the reaction was mainly controlled by diffusion. For a more precise consideration of the diffusion effect, a diffusion factor was added to Kamal's equation. In this way, the curing kinetics were predicted well over the entire range of conversions, covering both the previtrification and postvitrification stages. The glass‐transition temperatures of the o‐CFER/DDE samples were determined via torsional braid analysis. The results showed that the glass‐transition temperatures increased with the curing temperature and conversion up to a constant value of approximately 370 K. The thermal degradation kinetics of the system were investigated with thermogravimetric analysis, which revealed two decomposition steps. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 182–188, 2004     

低温固化改性BMI树脂基体动力学研究

采用催化剂、3,3′-二烯丙基双酚A(DP)和多官能团单体C改性4,4′-二氨基二苯甲烷双马来酰亚胺(BMI)树脂,制取低温固化、高温性能优良的改性BMI树脂。采用差示扫描量热法(DSC)研究了改性BMI树脂的固化反应动力学,计算了固化反应体系的动力学参数,进而提出了该改性BMI树脂固化成型过程的动力学模型,并结合傅里叶红外光谱(FT-IR)对反应机理进行了探讨。研究结果表明,催化剂对固化反应的进行有重要的促进作用,改性BMI树脂的固化温度由259℃降为178℃;烯丙基与马来酰亚胺基的"ene"反应非常显著,且改性剂C与DP的"ene"反应历程相似;改性BMI树脂的固化工艺确定为120℃×6h+140℃×2h+160℃×2h+180℃×2h,后处理工艺为200℃×6h。     

Curing behavior study of polydimethylsiloxane‐modified allylated novolac/4,4′‐bismaleimidodiphenylmethane resin

The curing behavior of polydimethylsiloxane‐modified allylated novolac/4,4′‐bismaleimidodiphenylmethane resin (PDMS‐modified AN/BDM) was investigated by using Fourier transform infrared spectrometry (FTIR) and differential scanning calorimetry. The results of FTIR confirmed that the curing reactions of the PDMS‐modified AN/BDM resins, including “Ene” reaction and Diels–Alder reaction between allyl groups and maleimide groups, should be similar to those of the parent allylated novolac/4,4′‐bismaleimidodiphenylmethane (AN/BDM) resin. The results of dynamic DSC showed that the total curing enthalpy of the PDMS‐modified AN/BDM resins was lower than that of the parent resin. Incorporation of polydimethylsiloxane (PDMS) into the backbone of the allylated novolac (AN) resin favored the Claisen rearrangement reaction of allyl groups. The isothermal DSC method was used to study the kinetics of the curing process. The experimental data for the parent AN/BDM resin and the PDMS‐modified AN/BDM resins exhibited an nth‐order behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Comparison of the curing kinetics of the RTM6 epoxy resin system using differential scanning calorimetry and a microwave‐heated calorimeter

The cure of a commercial epoxy resin system, RTM6, was investigated using a conventional differential scanning calorimeter and a microwave‐heated calorimeter. Two curing methods, dynamic and isothermal, were carried out and the degree of cure and the reaction rates were compared. Several kinetics models ranging from a simple nth order model to more complicated models comprising nth order and autocatalytic kinetics models were used to describe the curing processes. The results showed that the resin cured isothermally showed similar cure times and final degree of cure using both conventional and microwave heating methods, suggesting similar curing mechanisms using both heating methods. The dynamic curing data were, however, different using two heating methods, possibly suggesting different curing mechanisms. Near‐infrared spectroscopy showed that in the dynamic curing of RTM6 using microwave heating, the epoxy‐amine reaction proceeded more rapidly than did the epoxy‐hydroxyl reaction. This was not the case during conventional curing of this resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3658–3668, 2006     

Curing kinetics and viscosity change of a two‐part epoxy resin during mold filling in resin‐transfer molding process

The curing kinetics and the resulting viscosity change of a two‐part epoxy/amine resin during the mold‐filling process of resin‐transfer molding (RTM) of composites was investigated. The curing kinetics of the epoxy/amine resin was analyzed in both the dynamic and the isothermal modes with differential scanning calorimetry (DSC). The dynamic viscosity of the resin at the same temperature as in the mold‐filling process was measured. The curing kinetics of the resin was described by a modified Kamal kinetic model, accounting for the autocatalytic and the diffusion‐control effect. An empirical model correlated the resin viscosity with temperature and the degree of cure was obtained. Predictions of the rate of reaction and the resulting viscosity change by the modified Kamal model and by the empirical model agreed well with the experimental data, respectively, over the temperature range 50–80°C and up to the degree of cure α = 0.4, which are suitable for the mold‐filling stage in the RTM process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2139–2148, 2000     

Cure kinetics of aqueous phenol–formaldehyde resins used for oriented strandboard manufacturing: Effect of zinc borate

The effect of zinc borate (ZB) on the cure kinetics of commercial phenol–formaldehyde oriented strandboard adhesives was studied using differential scanning calorimetry. ZB caused a separation of the addition and condensation reactions for both face and core resin (CR) systems with lowered cure temperature for the addition reaction. For the face resin, ZB did not change its nth‐order curing mechanism, but retarded the whole cure reactions, and increased the reaction order and the activation energy. Compared with neat CR, the addition reaction of the CR/ZB mixture, which occurred at temperatures lower than 60°C, also followed an nth‐order reaction mechanism. The condensation reaction of the mixture was changed from an autocatalytic reaction to an nth‐order one with the reaction order of about 1. The proposed models fitted the experimental data well. Relationships among cure reaction conversion (i.e., cure degree), cure temperature, and cure time were predicted for various resin/ZB systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3886–3894, 2006     

改性BMI/苯并噁嗪树脂的固化反应及其动力学研究

将改性双马来酰亚胺(BMI)树脂与苯并噁嗪(B-a)树脂进行共混共聚制备了改性BMI/B-a树脂,采用动态DSC技术研究了改性BMI/B-a树脂的固化反应过程。实验结果表明,在100～350℃范围内出现两个峰,其中100～153℃是树脂的熔融吸热峰(峰顶温度为134℃),156～303℃是树脂固化反应过程的放热峰(峰顶温度为232℃);改性BMI树脂与B-a树脂的固化反应级数为0.93,活化能为85.6 kJ/mol;改性BMI/B-a树脂的固化工艺为180℃×1 h+200℃×2 h+230℃×2 h,后处理工艺为280℃×2 h。     

Reaction kinetics,thermal properties of tetramethyl biphenyl epoxy resin cured with aromatic diamine

Epoxy resins, 4, 4′‐diglycidyl (3, 3′, 5, 5′‐tetramethylbiphenyl) epoxy resin (TMBP) containing rigid rod structure as a class of high performance polymers has been researched. The investigation of cure kinetics of TMBP and diglycidyl ether of bisphenol‐A epoxy resin (DGEBA) cured with p‐phenylenediamine (PDA) was performed by differential scanning calorimeter using an isoconversional method with dynamic conditions. The effect of the molar ratios of TMBP to PDA on the cure reaction kinetics was studied. The results showed that the curing of epoxy resins contains different stages. The activation energy was dependent of the degree of conversion. At the early of curing stages, the activation energy showed the activation energy took as maximum value. The effects of rigid rod groups and molar ratios of TMBP to PDA for the thermal properties were investigated by the DSC, DMA and TGA. The cured 2/1 TMBP/PDA system with rigid rod groups and high crosslink density had shown highest T_g and thermal degradation temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

动态DSC法研究BMI改性酚醛树脂固化反应动力学

采用非等温DSC(差示扫描量热)法研究BMI(双马来酰亚胺)改性PF(酚醛树脂)体系的固化动力学,借助升温速率-温度(β-T)外推法和红外光谱(FT-IR)跟踪固化反应过程,确定了BAN(BMI改性PF)体系的固化工艺和固化动力学参数。结果表明:BAN的固化工艺为"120℃/2 h→140℃/2 h→160℃/2 h→180℃/2 h",后处理工艺为220℃/3 h,BAN固化体系的动力学参数是表观活化能Ea=123.4 kJ/mol、频率因子A=1.96×1012s-1和反应级数n=1.05;根据n级动力学反应模型求解出该树脂的反应动力学方程,其计算值与试验值基本吻合,说明该模型能较好描述BAN的固化反应过程。     

A kinetic study on the autocatalytic cure reaction of a cyanate ester resin

The cure of a novolac‐type cyanate ester monomer, which reacts to form a polycyanurate network, was investigated by using differential scanning calorimeter. The conversions and the rates of cure were determined from the exothermic curves at several isothermal temperatures (513–553 K). The experimental data, showing an autocatalytic behavior, conforms to the kinetic model proposed by Kamal, which includes two reaction orders, m and n, and two rate constants, k₁ and k₂. These kinetic parameters for each curing temperature were obtained by using Kenny's graphic‐analytical technique. The overall reaction order was about 1.99 (m = 0.99, n = 1.0) and the activation energies for the rate constants, k₁ and k₂, were 80.9 and 82.3 kJ/mol, respectively. The results show that the autocatalytic model predicted the curing kinetics very well at high curing temperatures. However, at low curing temperatures, deviation from experimental data was observed after gelation occurred. The kinetic model was, therefore, modified to predict the cure kinetics over the whole range of conversion. After modification, the overall reaction order slightly decreased to be 1.94 (m = 0.95, n = 0.99), and the activation energies for the rate constants, k₁ and k₂, were found to be 86.4 and 80.2 kJ/mol. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3067–3079, 2004     

Cure kinetics of aqueous phenol–formaldehyde resins used for oriented strandboard manufacturing: Analytical technique

The cure kinetics of commercial phenol–formaldehyde (PF), used as oriented strandboard face and core resins, were studied using isothermal and dynamic differential scanning calorimetry (DSC). The cure of the face resin completely followed an nth‐order reaction mechanism. The reaction order was nearly 1 with activation energy of 79.29 kJ mol^?1. The core resin showed a more complicated cure mechanism, including both nth‐order and autocatalytic reactions. The nth‐order part, with reaction order of 2.38, began at lower temperatures, but the reaction rate of the autocatalytic part increased much faster with increase in curing temperature. The total reaction order for the autocatalytic part was about 5. Cure kinetic models, for both face and core resins, were developed. It is shown that the models fitted experimental data well, and that the isothermal DSC was much more reliable than the dynamic DSC in studying the cure kinetics. Furthermore, the relationships among cure reaction conversion (curing degree), cure temperature, and cure time were predicted for both resin systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1642–1650, 2006