Non‐isothermal degradation kinetics of N,N′‐bismaleimide‐4,4′‐diphenylmethane/barbituric acid based polymers in the presence of hydroquinone

The non‐isothermal degradation kinetics of the cured polymer samples of N,N′‐bismaleimide‐4,4′‐diphenylmethane/barbituric acid [BMI/BTA = 2/1 (mol/mol)] based polymers in the presence of hydroquinone (HQ) and native BMI/BTA was investigated by the thermogravimetric (TG) technique. By adding 5 wt % HQ into the BMI/BTA polymerization, the activation energy (E_a) of the thermal degradation process increased significantly in comparison with native BMI/BTA. Thus, the thermal stability of the cured polymer sample in the presence of HQ was greatly improved. The thermal degradation process exhibits three distinct stages. The key kinetic parameters associated with these stages were attained via the model‐fitting method. For the sample of native BMI/BTA, the thermal degradation process was primarily controlled by nucleation, followed by the multi‐decay law in the first stage. In contrast, the reaction order model adequately described the thermal degradation kinetics in the second stage. As to the last stage, the complex processes were described satisfactorily by the best‐fitted reaction model. For the sample of BMI/BTA/5 wt % HQ, the degradation process was controlled by the nucleation mechanism, followed by the multi‐molecular decay law in the first stage. In contrast, the second stage was controlled by the mixed mode of the competitive reaction order mechanism and 3‐D diffusion mechanism. In the third stage, the complex processes were also adequately described by the best‐fitted reaction model. All the experimental results illustrated that incorporation of 5 wt % HQ into the BMI/BTA based polymer resulted in the best thermal stability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1923–1930, 2013     

Decoration of graphene oxide nanosheets with amino silane‐functionalized silica nanoparticles for enhancing thermal and mechanical properties of polypropylene nanocomposites

Graphene oxide nanosheets were decorated by amino‐silane modified silica nanoparticles. An electrostatic interaction between the negative charge of oxygen‐containing groups of graphene oxide and the positive charge of amino‐silane functional groups on the surface of silica nanoparticles plays a major role for the interfacial interaction of these two materials. The hybrid material was then used as a reinforcement in polypropylene (PP) composite. The increasing tensile strength at yield, tensile, and flexural modulus of the PP composite at a graphene oxide‐ amino‐silane silica loading content of 20 wt % are about 24.81, 55.52, and 30.35%, respectively, when compared with those of PP. It is believed that GO assists the dispersion of SiO₂ nanoparticles to the polymer matrix because of its unique structure having hydrophilicity due to its oxygen functional groups and hydrophobicity owing to its backbone graphitic carbon structure. This hybrid material may also be used as the reinforcement in other polyolefins. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44382.     

Synthesis and characterization of phenylsiloxane‐modified bismaleimide/barbituric acid‐based polymers with 3‐aminopropyltriethoxysilane as the coupling agent

The preparation and characterization of phenylsiloxane (PhSLX)‐modified N,N′‐bismaleimide‐4,4′‐diphenylmethane (BMI)/barbituric acid (BTA) (10/1 mol/mol) oligomers are described. 3‐Aminopropyltriethoxysilane (APTES) was used as the coupling agent. The resultant hybrid BMI/BTA‐APTES‐PhSLX polymers were characterized primarily using thermogravimetric analysis in combination with differential scanning calorimetry and Fourier transform infrared measurements. The thermal stability of the BMI/BTA oligomer was improved significantly by incorporation of a small amount (20–30 wt%) of the copolymer of PhSLX and APTES (PASi). After adequate post‐curing reactions, the PASi‐modified BMI/BTA oligomers (HYBRID20 and HYBRID30 containing 20 and 30 wt% PASi, respectively) exhibited greatly reduced thermal degradation rates in the temperature range 300–800 °C and an increased level of residues at 800 °C as compared to the native BMI/BTA oligomer. This was further confirmed by thermal degradation kinetic studies, in which the activation energies for the thermal degradation reactions of the cured PASi‐modified BMI/BTA oligomers were shown to be higher than that of the pristine BMI/BTA oligomer. © 2012 Society of Chemical Industry     

Preparation and characterization of bismaleimide (N,N′‐bismaleimido‐4,4′‐diphenyl methane)–vinyl ester oligomer–modified unsaturated polyester interpenetrating matrices for advanced composites

Interpenetrating networks of varying percentages of bismaleimide (BMI) in vinyl ester oligomer (VEO) modified unsaturated polyester (UP) matrices have been developed. Vinyl ester oligomer was prepared by reacting commercially available epoxy resin GY 250 (Ciba‐Geigy) and acrylic acid, and used as a toughening agent for unsaturated polyester resin. Unsaturated polyesters modified with 10, 20, and 30 wt % vinyl ester oligomer were made. The VEO toughened unsaturated polyester matrix systems, further modified with 5, 10, and 15 wt % bismaleimide (BMI). BMI–VEO–UP matrices were characterized using differential scanning calorimetry, thermogravimetric analysis, and heat deflection temperature analysis. The matrices, in the form of castings, were characterized for their mechanical properties according to ASTM methods: tensile strength, flexural strength, and unnotched Izod impact test. Data obtained from mechanical studies and thermal characterization indicate that the introduction of VEO and BMI into unsaturated polyester resin improves thermomechanical properties according to their percentage concentration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2502–2508, 2002     

Tribological properties of bismaleimide composites with surface‐modified SiO2 nanoparticles

In this article, the surface of SiO₂ nanoparticles was modified by silane coupling agent N‐(2‐aminoethyl)‐γ‐aminopropylmethyl dimethoxy silane. The bismaleimide nanocomposites with surface‐modified SiO₂ nanoparticles or unmodified SiO₂ nanoparticles were prepared by the same casting method. The tribological performance of the nanocomposites was studied on an M‐200 friction and wear tester. The results indicated that the addition of SiO₂ nanoparticles could decrease the frictional coefficient and the wear rate of the composites. The nanocomposites with surface‐modified SiO₂ nanoparticles showed better wear resistance and lower frictional coefficient than that with the unmodified nanoparticles SiO₂. The specific wear rate and the steady frictional coefficient of the composite with 1.0 wt % surface‐modified SiO₂ nanoparticles are only 1.8 × 10^?6 mm³/N m and 0.21, respectively. The dispersion of surface‐modified SiO₂ nanoparticles in resin matrix was observed with transmission electron microscope, and the worn surfaces of pure resin matrix and the nanocomposites were observed with scanning electron microscope. The different tribological behavior of the resin matrix and the filled composites should be dependent on their different mechanical properties and wear mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermally and mechanically enhanced epoxy resin‐silica hybrid materials containing primary amine‐modified silica nanoparticles

In this article, a series of hybrid materials consisted of epoxy resin matrix and well‐dispersed amino‐modified silica (denoted by AMS) nanoparticles were successfully prepared. First of all, the AMS nanoparticles were synthesized by performing the conventional acid‐catalyzed sol–gel reactions of tetraethyl orthosilicate (TEOS), which acts as acceded sol–gel precursor in the presence of 3‐aminopropyl trimethoxysilane (APTES), a silane coupling agent molecules. The as‐prepared AMS nanoparticles were then characterized by FTIR, ¹³C‐NMR, and ²⁹Si‐NMR spectroscopy. Subsequently, a series of hybrid materials were prepared by performing in situ thermal ring‐opening polymerization reactions of epoxy resin in the presence of as‐prepared AMS nanoparticles and raw silica (RS) particles (i.e., pristine silica). AMS nanoparticles were found to show better dispersion capability in the polymer matrices than that of RS particles based on the morphological observation of transmission electron microscopy (TEM) study. The better dispersion capability of AMS nanoparticles in hybrid materials was found to lead enhanced thermal, mechanical properties, reduced moisture absorption, and gas permeability based on the measurements of thermo gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and gas permeability analysis (GPA), respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of superhydrophobic nanocomposite fiber membranes by electrospinning poly(vinylidene fluoride)/silane coupling agent modified SiO2 nanoparticles

Superhydrophobic nanocomposite fiber membranes were prepared by blend electrospinning of poly(vinylidene fluoride) (PVDF) mixed with silane coupling agent modified SiO₂ nanoparticles. The nanoparticles were prepared by the sol–gel method, and the average particle diameter was measured by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The effects of the type of silane coupling agent, such as n‐octyltriethoxysilane, vinyltrimethoxysilane (A‐171), and vinyltriethoxysilane (A‐151), and the mass ratio of the modified silica particles and PVDF on the surface wettability of the composite fiber membrane were investigated. The results indicated that the incorporation of silane coupling agent modified silica particles into the PVDF membrane increased the roughness of the surface and formed micro/nano dual‐scale structure compared to the pristine PVDF membrane, which was responsible for the superhydrophobicity and self‐cleaning property of the nanocomposite fiber membranes. The value of water contact angle (CA) increased with the increase of the content of modified SiO₂ nanoparticles in the nanocomposite membrane, ranging from 149.8° to 160.1° as the mass ratio of modified 170 nm SiO₂ with PVDF matrix increased from 0.5:1 to 5:1, indicating the membrane possesses a superhydrophobic surface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44501.     

Effects of silica nanoparticles on tribology performance of poly(Epoxy Resin‐Bismaleimide)‐based nanocomposites

Introduction of small nanoparticles into polymer matrix increases the mechanical, tribological, and thermal properties of nanocomposites. In this study, poly(epoxy resin‐bismaleimide‐diaminodiphenylmethane) (EP‐BMI‐DDM) copolymers filled with silica nanoparticles (SNPs) were successfully fabricated through in situ suspension polymerization. To enhance the interfacial adhesion of silica particles to the polymer matrix, the nanoparticles were organo‐modified by silane coupling agent. Results of tensile strength test revealed that increased toughness of the composites was attributed to the microcavitations induced by organo‐modified SNPs (OSNPs). Proper loadings of OSNPs can play a critical role in antifriction performance, with optimal friction coefficient of 0.17 (2 wt% OSNPs content). Thermostabilities of the nanocomposites were characterized by differential thermal gravimetric analysis. At the maximum rate of weight loss of EP‐BMI‐DDM/3 wt% OSNP, the temperature measured 452°C, which is 52°C higher than that of pure EP‐BMI‐DDM copolymers (400°C). The produced nanocomposites feature good thermostability and self‐lubrication can be widely used as wearable material under severe working conditions with higher temperature. POLYM. ENG. SCI., 59:274–283, 2019. © 2018 Society of Plastics Engineers     

Studies on mechanical,thermal, and morphology of diglycidylether‐terminated polydimethylsiloxane‐modified epoxy–bismaleimide matrices

An epoxy matrix system modified by diglycidylether‐terminated polydimethylsiloxane (DGETPDMS) and bismaleimide (BMI) was developed. Epoxy systems modified with 4, 8, and 12% (by wt) of DGETPDMS were made using epoxy resin and DGETPDMS, with diaminodiphenylmethane as the curing agent. The DGETPDMS‐toughened epoxy systems were further modified with 4, 8, and 12% (by wt) of BMI, namely (N,N′‐bismaleimido‐4,4′‐diphenylmethane). DGETPDMS/BMI/epoxy matrices were characterized using differential scanning calorimetry, thermogravimetric analysis, and heat deflection temperature analysis. The matrices, in the form of castings, were characterized for their mechanical properties, viz. tensile strength, flexural strength, and impact test, as per ASTM methods. Mechanical studies indicate that the introduction of DGETPDMS into epoxy resin improves the impact strength, with reduction in tensile strength, flexural strength, and glass transition temperature, whereas the incorporation of BMI into epoxy resin enhances the mechanical and thermal properties according to its percentage content. However, the introduction of both DGETPDMS and BMI enhances the values of thermomechanical properties according to their percentage content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 668–674, 2006     

Poly(vinyl chloride‐co‐vinyl acetate‐co‐maleic anhydride)/silica nanocomposites derived from in situ suspension polymerization

Poly(vinyl chloride‐co‐vinyl acetate‐co‐maleic anhydride) (PVVM)/silica nanocomposites were prepared by the suspension radical copolymerization of the monomers in the presence of fumed silica premodified with γ‐methylacryloxypropl trimethoxy siliane. Morphological observation showed that the silica particles of nanometer scale were well dispersed in the copolymer matrix of the nanocomposites films, whereas silica particles tended to agglomerate in the composites films prepared by the solution blending of PVVM with silica. The experimental results show that the thermal stability, glass‐transition temperature, tensile strength, and Young's modulus were significantly enhanced by the incorporation of silica nanoparticles. The enhancement of properties was related to the better dispersion of silica particles in polymer matrix and the interaction between the polymer chains and the surfaces of the silica particles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of the structure of silane‐coupling agent on dynamic mechanical properties of dental resin‐nanocomposites

This work was aimed at the study by dynamic mechanical analysis (DMA) of dental composites consisted of a Bis‐GMA/TEGDMA (50/50 wt/wt) matrix and silica nanoparticles (Aerosil OX50) as filler, silanized with various silanes. The silanes used were 3‐[(1,3(2)‐dimethacryloyloxypropyl)‐2 (3)‐oxycarbonylamido] propyltriethoxy‐silane (UDMS), 3‐methacryloxypropyl‐trimethoxysilane (MPS), octyltrimethoxysilane (OTMS), blends of UDMS/OTMS (50/50 wt/wt), or MPS/OTMS (50/50 wt/wt). The total amount of silane was kept constant at 10% by weight fraction relative to the filler weight. The silanized nanoparticles were mixed with the dimethacrylate matrix (60% filler by weight fraction). The composites were light cured and tested by DMA for the determination of storage modulus (E′), loss modulus (E″), tangent delta (tan δ), and glass transition temperature (T_g). Measurements were performed in samples immediately after curing and samples stored in water at 37°C for 1, 7, 30, or 120 days. OTMS‐composite in which OTMS does not form covalent bond with the dimethacrylate matrix showed lower elastic modulus both in dry and wet conditions. The ability of bifunctional UDMS for crosslinking was found not to increase the elastic behavior of the composite, as it was expected, compared with that of MPS‐composite, because of the high amount of the silane used. After immersion in water the elastic modulus of OTMS‐composite remained constant, while that of the other composites increased after 1 day and then remained constant up to 120 days. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and antibacterial effects of PVA‐PVP hydrogels containing silver nanoparticles

The poly(vinyl alcohol)/poly(N‐vinyl pyrrolidone) (PVA–PVP) hydrogels containing silver nanoparticles were prepared by repeated freezing–thawing treatment. The silver content in the solid composition was in the range of 0.1–1.0 wt %, the silver particle size was from 20 to 100 nm, and the weight ratio of PVA to PVP was 70 : 30. The influence of silver nanoparticles on the properties of PVA–PVP matrix was investigated by differential scanning calorimeter, infrared spectroscopy and UV–vis spectroscopy, using PVA–PVP films containing silver particles as a model. The morphology of freeze‐dried PVA–PVP hydrogel matrix and dispersion of the silver nanoparticles in the matrix was examined by scanning electron microscopy. It was found that a three‐dimensional structure was formed during the process of freezing–thawing treatment and no serious aggregation of the silver nanoparticles occurred. Water absorption properties, release of silver ions from the hydrogels and the antibacterial effects of the hydrogels against Escherichia coli and Staphylococcus aureus were examined too. It was proved that the nanosilver‐containing hydrogels had an excellent antibacterial ability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 125–133, 2007     

Solid‐phase preparation method of silica‐supported 2,2′‐methylenebis(6‐tert‐butyl‐4‐methyl‐phenol) and its antioxidative behavior in styrene‐butadiene rubber

A solid‐phase preparation method is applied to the synthesis of a novel supported rubber antioxidant, silica–supported 2,2′‐methylenebis(6‐tert‐butyl‐4‐methyl‐phenol) (SiO₂‐2246), by directly reacting 2,2′‐methylenebis (6‐tert‐butyl‐4‐methyl‐phenol)(antioxidant 2246) with silica. FTIR, Raman spectroscopy and TGA confirm that the antioxidant 2246 is chemically bonded on the surface of the silica particles. The SEM observation shows that the SiO₂‐2246 is homogeneously dispersed in the styrene‐butadiene rubber (SBR) matrix. The results of the apparent activation energy and the attenuated total reflectance infrared spectrometry indicate that the antioxidative efficiency of the SiO₂‐2246 in SBR is superior to the corresponding low‐molecular‐weight 2246. The thermal oxidative stability of the SBR/SiO₂‐2246 composites is much higher than that of the SBR/SiO₂/2246 composites by comparing their mechanical properties retentions and crosslinking densities. Additionally, the advantages of SiO₂‐2246 also include low migration, low volatility, and low pollution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43014.     

Cure kinetics of multifunctional epoxies with 2,2′‐dichloro‐4,4′‐diaminodiphenylmethane as hardener

The curing behavior of the epoxy resin N,N,N′,N′‐tetraglycidyldiaminodiphenyl methane (TGDDM) with triglycidyl p‐aminophenol as a reactive diluent was investigated using 2,2′‐dichloro‐4,4′‐diaminodiphenylmethane (DCDDM) as the curing agent. The effect of the curing agent on the kinetics of curing, shelf‐life, and thermal stability in comparison with a TGDDM‐diaminodiphenylsulfone (DDS) system was studied. The results showed a lesser activation energy at the lower level of conversion with a broader cure exotherm for the epoxy‐DCDDM system in comparison with the epoxy‐DDS system, although the overall activation energy for the two systems was comparable. TGA studies showed more stability in the epoxy‐DCDDM system than in the epoxy‐DDS system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2097–2103, 2000     

Effects of solvent basicity on free radical polymerizations of N,N′‐bismaleimide‐4,4′‐diphenylmethane initiated by barbituric acid

The polymerizations of N,N′‐bismaleimide‐4,4′‐diphenylmethane (BMI) initiated by barbituric acid (BTA) carried out in a variety of solvents at 130°C were studied. The nitrogen‐containing cyclic solvents such as N‐methyl‐2‐pyrrolidinone acted as a catalyst to promote the formation of the three‐dimensional crosslinked network structure. By contrast, the polymerization in a cyclic solvent that did not contain nitrogen such as γ‐butyrolactone resulted in nil gel content. The higher the solvent basicity, the larger the amount of insoluble polymer species formed. The molar ratio of BTA to BMI also played an important role in the polymerizations. The resultant polymers, presumably having a hyper‐branched structure, exhibited much narrower molecular weight distributions than those prepared by conventional free radical polymerizations. The BMI polymerizations using BTA as the initiator could not be adequately described by conventional free radical polymerization mechanisms. A polymerization mechanism that took into account the generation of a ketone radical pair between BTA and BMI and the subsequent initiation, propagation and termination reactions was proposed. It was concluded that the nitrogen‐containing cyclic solvents were capable of participating in the ketone radical pair formation process, thereby increasing the extent of polymer crosslinking reactions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphologically dependent alternating‐current and direct‐current breakdown strength in silica–polypropylene nanocomposites

In this article, we report the synthesis of a new bimodal surface ligand morphology on silica nanoparticles. Combining grafting‐to and grafting‐from approaches, in this study, we demonstrated the efficacy of anthracene surface modification for improving the dielectric breakdown strength (DBS) under alternating‐current and direct‐current conditions and that of a matrix‐compatible polymer brush for controlling the nanofiller (NF) dispersion. Ligand‐modified spherical colloidal SiO₂ nanoparticles (～14 nm in diameter) were mixed into polypropylene, and the resulting dispersion was improved over the unmodified particles, as shown with transmission electron microscopy. The results suggest that the electronic structure of the anthracene‐modified particle surface was critical to the improvement in DBS. In addition, the DBS of the composite was shown to depend on the dispersion state of the filler and the mode of stress; this indicated that the individually dispersed nanoparticles were not necessarily the optimal morphology for all stress conditions. Additionally, the precise nature of the matrix‐compatible brush was less important than the NF dispersion it produced. The bimodal grafted architectural design has provided a promising solution for the control of the dispersion and surface properties, especially for high‐molecular‐weight polymer matrices. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44347.     

Effect of Silica‐Coated Poly(butyl methacrylate)‐block‐poly(methyl methacrylate) Double‐Shell Particles on the Mechanical Properties of PMMA Composites

Silica nanoparticles with an average diameter of 12 nm are grafted with PBMA‐b‐PMMA double shells through typical sequential ATRP from bromoisobutyrate initiators anchored at the silica surface using an epoxysilane. A commercially available PMMA homopolymer is used for the preparation of composites with unmodified, silane‐modified and double‐shell‐modified silica particles. Good mechanical properties are obtained for silica double shell containing systems. The silica content in double shell particle systems is varied from 0 to 2.5 wt%. A significant improvement in impact properties is observed. The surface‐modified silica particles are characterized by ATR‐FTIR, NMR, GPC, and thermal analyses. TEM analysis is used to analyze the nature of dispersion of particles in the composites.

     

Surface‐modified silica nanoparticles for reinforcement of PMMA

Polymethyl methacrylate (PMMA) was introduced onto the surface of silica nanoparticles by particle pretreatment using silane coupling agent (γ‐methacryloxypropyl trimethoxy silane, KH570) followed by solution polymerization. The modified silica nanoparticles were characterized by Fourier‐transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Sedimentation tests and lipophilic degree (LD) measurements were also performed to observe the compatibility between the modified silica nanoparticles and organic solvents. Thereafter, the PMMA slices reinforced by silica‐nanoparticle were prepared by in situ bulk polymerization using modified silica nanoparticles accompanied with an initiator. The resultant polymers were characterized by UV–vis, Sclerometer, differential scanning calorimetry (DSC). The mechanical properties of the hybrid materials were measured. The results showed that the glass transition temperature, surface hardness, flexural strength as well as impact strength of the silica‐nanoparticle reinforced PMMA slices were improved. Moreover, the tensile properties of PMMA films doped with silica nanoparticles via solution blending were enhanced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Kinetics of Michael addition polymerizations of n,n′‐bismaleimide‐4,4′‐diphenylmethane with barbituric acid

With the addition of sufficient hydroquinone to completely suppress the free radical polymerization, the kinetics of Michael addition polymerizations of N,N′‐bismaleimide‐4,4′‐diphenylmethane (BMI) and barbituric acid (BTA) with BMI/BTA = 2/1 (mol/mol) in 1‐methyl‐2‐pyrrolidone was investigated independently. A mechanistic model was developed to adequately predict the polymerization kinetics before a critical conversion (ca. 60%), at which point the diffusion‐controlled polymer reactions started to predominate in the latter stage of polymerization. The Michael addition polymerization rate constants and activation energy in the temperature range 383–423 K were determined accordingly. Beyond the critical conversion, a relatively stationary limiting conversion (ca. 69%) independent of the reaction temperature was achieved. A diffusion‐controlled polymerization model taken from the literature satisfactorily predicted the limiting conversion data. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Kinetic and structural studies of the polymerization of N,N′‐bismaleimide‐4,4′‐diphenylmethane with barbituric acid

Both the isothermal and non‐isothermal polymerizations of N,N′‐bismaleimide‐4,4′‐diphenylmethane (BMI) with barbituric acid (BTA) were investigated by the differential scanning calorimeter. The experimental results showed that the polymerizations of BMI with BTA were governed by the competitive Michael addition reaction and free radical polymerization mechanisms. Furthermore, the contribution of free radical polymerization becomes more important when the mole fraction of BTA decreases. ¹H NMR and ¹³C NMR measurements further support the coexistence of the Michael addition reaction and free radical polymerization mechanisms. A preliminary kinetic model that took into account the competitive Michael addition reaction and free radical polymerization mechanisms was developed. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers