Allylated novolac/4,4′‐bismaleimidodiphenylmethane resin containing polyhedral oligomeric silsesquioxane: Preparation,morphology and thermal stability

Allylated novolac/4,4′‐bismaleimidodiphenylmethane resin (AN/BDM) had been modified with well‐defined inorganic building blocks‐polyhedral oligomeric silsesquioxane (POSS). Octamaleimidophenyl polyhedral silsesquioxane (OMPS) was used as the cocuring reagent of the AN/BDM resin to prepare POSS‐modified AN/BDM resin, and POSS content was between 0 and 17.8 wt %. The curing reaction of the POSS‐modified AN/BDM resin was monitored by means of Fourier transform infrared spectroscopy (FTIR), and the results revealed that maleimide groups on OMPS molecule could undergothe curing reaction between allyl groups and maleimide groups. Therefore, the crosslinked network containing POSS was formed. Scanning electron microscopy (SEM) and X‐ray diffraction (XRD) were employed to study the morphology of the cured POSS‐modified AN/BDM resins. The homogeneous dispersion of POSS cages in AN/BDM matrices was evidenced. Thermogravimetric analysis (TGA) indicated that incorporation of POSS into AN/BDM crosslinked network led to enhanced thermal stability. The improved thermal stability could be ascribed to higher crosslink density and inorganic nature of POSS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3903–3908, 2007     

High‐performance hyperbranched poly(phenylene oxide) modified bismaleimide resin with high thermal stability,low dielectric constant and loss

High‐performance hyperbranched poly(phenylene oxide)‐modified bismaleimide resin with high thermal stability, low dielectric constant, and loss was developed, which is made up of hyperbranched poly(phenylene oxide) (HBPPO), 4,4′‐bismaleimidodiphenylmethane (BDM), and o, o′‐diallylbisphenol A (DBA). The curing reactivity, morphology, and performance of BDM/DBA/HBPPO resin were systemically investigated, and similar investigations for BDM/DBA resin were also carried out for comparison. Results show that BDM/DBA/HBPPO and BDM/DBA resins have similar curing mechanism, but the former can be cured at lower temperature than the later; in addition, cured BDM/DBA/HBPPO resin with suitable HBPPO content has better thermal stability and dielectric properties (lower dielectric constant and loss) than BDM/DBA resin. The difference in macroproperties between BDM/DBA/HBPPO and BDM/DBA resins results from the different chemical structures and morphologies of their crosslinking networks. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effect of allylation degree on processing properties,thermal cure,and thermal properties of BMAN resins

A series of allyl‐functional novolac (AN) resins with various allylation degree, from 32.4 to 114.6%, were synthesized and blended reactively with 4,4′‐bismaleimide biphenyl methane (BMI) at a weight ratio of 2.50 : 1 to get BMI‐modified and allyl‐functional novolac (BMAN) resins. Structural characteristics of the resins were determined by Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (¹HNMR) techniques. Processing properties of BMAN resin system was evaluated by solubility, rheology, and thermal gelation, and the results show that processing properties of BMAN resins were excellent and could be tailored by changing allylation degree of AN resins. Differential scanning calorimetry (DSC) was used to evaluate cure reactivity of BMAN resin system, and the results reveal that the resins with higher allylation degree possessed better cure reactivity. Thermal properties were evaluated by means of dynamic mechanical analysis (DMA) and thermogravimetry analysis (TGA) techniques. The results reveal that with increase in allylation degree of resins the thermal stability of BMAN resins increased because of increase in crosslinking density, but char‐yields of the above resins at 800°C decreased in turn. Understanding of the relationship between allylation degree and properties of the resins would be useful to direct the design of material to meet different requirements of applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

烯丙基酚醛改性双马来酰亚胺树脂的制备与性能

合成并表征了烯丙基酚醛树脂,再将其与双马来酰亚胺共聚制备了烯丙基酚醛改性双马树脂。通过DSC和FTIR分析了该树脂的固化行为,研究了其工艺性,利用TGA和DMA评价了其固化物的耐热性。结果表明,烯丙基酚醛树脂改性双马树脂可用于RTM等成型工艺,其固化物Tg约为330℃,初始热分解温度约400℃,5%失重温度达410℃,10%失重温度423℃。该树脂耐热性优异,可用作耐高温先进复合材料的基体树脂。     

Study on Properties of Low Dieletric loss Resin Matrix

Summary One new high performance modified BMI resin matrix with enhanced processing characteristics, made from 4,4-bismaleimidodiphenyl methane (BDM) and allyl phenyl compounds, allyl epoxy resins and epoxy acrylate resins, were developed. Solubility, differential scanning calorimetry (DSC), gel time, and Fourier transform infrared (FTIR) spectroscopy were used to detect the structure and processing characteristics of the modified BMI resin and neat BDM. Results show that the new modified BMI resin systems have enhanced processability compared with neat BDM, especially improved solubility and faster thermal polymerization rate. In addition, the new cured systems have more than two times improved impact strength without a great decrease in excellent dielectric properties or thermal and hot–wet resistance of neat BDM resin.     

Blended resins based on a new propargyl‐functional resin: Synthesis,cure, and thermal properties

A new propargyl‐functional resin, propargyl ether bisphenol A novolac (PBPN), was synthesized, and the structure of PBPN were characterized using ¹H NMR and FTIR spectra. The PBPN was blended with 4,4′‐bismaleimide diphenyl methane (BDM) at different molar ratio to obtain the blends. Differential scanning calorimetry (DSC) was used to characterize the cure behavior of PBPN and the blends. Thermal gravimetric analysis (TGA) and dynamic mechanical analysis (DMA) were performed, respectively, to evaluate thermal stability and dynamic mechanical properties of the cured resins. The results indicate that the PBPN presented better cure and thermal properties than do traditional propargyl resins; furthermore, the cure behavior and thermal properties of PBPN could be improved remarkably by blending with BDM. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4207–4212, 2006     

Morphology transition of bismaleimide‐modified novolac resin

The bismaleimide (BMI)‐modified novolac resin was synthesized by allylation of the novolac resin and its “Ene” reaction with BMI. The reactions were monitored by Fourier transform infrared analysis (FTIR). The morphology of the BMI‐modified novolac resin changed with degree of allylation (i.e., the amount of BMI used). On the basis of the studies done by dynamical mechanical analysis (DMA), differential scanning calorimetry (DSC), and field emission scanning electron microscopy (FE‐SEM), it was found that when the degree of allylation increased from 48 to 59%, the resin changed from a single‐phase structure to a two‐phase structure. From the research by thermogravimetric analysis (TGA) and DMA, it was found that the higher allyl‐content (when > 48%) caused a decrease of the thermal properties and mechanical properties of the resultant resin. The BMI‐modified allyl novolac resin with 48% degree of allylation has the best thermal properties and the highest dynamic modulus in the current research. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 76–83, 2006     

Bis[4‐(4‐maleimidephen‐oxy)phenyl]propane/N,N‐4,4′‐bismaleimidodiphenylmethyene blend modified with diallyl bisphenol A

In this article, 2,2′‐bis[4‐(4‐maleimidephen‐oxy)phenyl)]propane (BMPP) resin and N,N‐4,4′‐bismaleimidodiphenylmethyene (BDM) resin blends were modified by diallyl bisphenol A (DABPA). The effects of the mole concentration of BMPP on mechanical properties, fracture toughness, and heat resistance of the modified resins were investigated. Scanning electron microscopy was used to study the microstructure of the fractured modified resins. The introduction of BMPP resin improves the fracture toughness and impact strength of the cured resins, whose thermal stabilities are hardly affected. Dynamic mechanical analysis shows that the modified resins can maintain good mechanical properties at 270.0°C, and their glass transition temperatures (T_g) are above 280.0°C. When the mole ratio of BDM : BMPP is 2 : 1(Code 3), the cured resin performs excellent thermal stability and mechanical property. Its T_g is 298°C, and the Charpy impact strength is 20.46 KJ/m². The plane strain critical stress intensity factor (K_IC) is 1.21 MPa·m^0.5 and the plane strain critical strain energy release rate (G_IC) is 295.64 J/m². Compared with that of BDM/DABPA system, the K_IC and G_IC values of Code 3 are improved by 34.07% and 68.10%, respectively, which show that the modified resin presented good fracture toughness. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40395.     

Synthesis of bismaleimide resin containing the poly(ethylene glycol) side chain: Curing behavior and thermal properties

Two maleimido end‐capped poly(ethylene glycol) (m‐PEG) of different molecular weights were synthesized and blended at various proportions with bismaleimide resin (4,4′‐bismaleimido diphenylmethane) (BDM). The curing behavior and the thermal properties of the m‐PEG/BDM blends were studied and presented here. It was found that the addition of m‐PEG enhanced the processability of the BDM resin significantly. The processing window of the BDM resin was increased from approximately 20 to 80°C. The addition of m‐PEG modified resins, however, resulted not only in the reduction in the thermal stability of the blended BDM resin but also elevation of the coefficients of thermal expansion. The changes in thermal/mechanical properties of the blends were found to be proportional to the amounts of m‐PEG incorporated. It was observed that the curing behavior, and thermal and mechanical properties, of the blends were independent of the molecular weight of the PEG segment. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2935–2945, 2002     

Building and origin of bio‐based bismaleimide resins with good processability,high thermal,and mechanical properties

Bio‐based high performance thermosetting resins have been urgently required by cutting‐edge fields for meeting sustainable development. A new kind of high performance thermosetting resins (BA‐n) with good processability, high thermal resistance, and mechanical properties was developed based on 4,4′‐bismaleimidodiphenylmethane (BDM) and renewable bis(5‐allyloxy)‐4‐methoxy‐2‐methylphenyl)methane (ABE) from bio‐based lignin derivative. The effect of the molar ratio of allyl to imide (n) on structures and properties of BA resins were systematically researched. BA‐n resins have much better processability, thermal, and mechanical properties than their petroleum‐based counterparts, 2,2′‐diallylbisphenol A‐modified BDM (BD‐n) resins. Compared with BD‐0.86, the best available bismaleimide (BMI) resin, BA‐0.86 not only has 6 h longer process window and 13.7 °C higher glass transition temperature, but also owns the highest flexural strength and modulus among all bio‐based allyl compound‐modified BMI resins reported. The origin behind these attractive performances of BA resins is revealed by discussing the unique crosslinked structure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45947.     

Flame‐retardant materials based on phosphorus‐containing polyhedral oligomeric silsesquioxane and bismaleimide/diallylbisphenol a with improved thermal resistance and dielectric properties

Polyhedral oligomeric silsesquioxane containing 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DP) was used to flame‐retard 4,4′‐bismaleimidophenyl methane (BDM)/2,2′‐dially bisphenol A (DBA) resins, and the integrated properties of the resins were investigated. The fire resistance of BDM/DBA resins containing DP was analyzed by limiting oxygen index (LOI) and vertical burning (UL94) tests. The results show that DP increased the LOI of the resins from 25.3 to 38.5%. The BDM/DBA resins were evaluated to have a UL‐94 V‐1 rating, which did not satisfy the high standards of industry. On the other hand, BDM/DBA containing DP achieved a UL‐94 V‐0 rating. The thermal stability and char formation were studied by thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy. TGA and scanning electron microscopy–energy‐dispersive X‐ray spectrometry measurements demonstrated that the DP resulted in an increase in the char yield and the formation of the thermally stable carbonaceous char. The results of Raman spectroscopy showed that the DP enhanced the graphitization degree of the resin during combustion. Moreover, the modified BDM/DBA resins exhibited improved dielectric properties. Specifically, the dielectric constant and loss at 1 MHz of the BDM/DBA/15% DP resin were 3.11 and 0.008, respectively, only about 93 and 73% of those of the BDM/DBA resin. All of the investigations showed that DP was an effective additive for developing high‐performance resins with attractive flame‐retardant and dielectric properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41545.     

Thermosetting matrices for composite materials based on allyl/propagryl substituted novolac resins

A new type of modified thermoset resins was synthesized by Williamson reaction from novolac resin and a mixture of allyl and propargyl chlorides of the different ratios with total allyl/propargyl substitution 50 %. The compositions of the resins were defined by nuclear magnetic resonance (¹H NMR) spectroscopy, and the dependence of the cured material properties on the composition was established. An increase of a propargyl content resulted in char yield raise, and the maximum value had been found for propargylated resin which was 60 %. By differential scanning calorimetry (DSC) analysis of the curing process, it was demonstrated that exothermic enthalpy could be adjusted by varying the content of propargyl and allyl groups in the resin. It was shown that the resin substituted with allyl only ether could not be cured without decomposition, but an introduction of propargyl groups in allyl ether-modified resin allowed to obtain cured samples and thus to develop a new type of thermosetting resins.     

Study on BMI modified allyl‐functional novolac resin/silica cloth composites: Effect of allylation degree on thermal and mechanical properties

A series of allyl‐functional novolac resin with various allylation degree, from 32.4 to 114.6%, were synthesized and then blended reactively with 4,4′‐bismaleimide biphenyl methane (BMI) at a weight ratio of 2.50:1 to get BMI‐modified allyl‐functional novolac (BMAN) resins. BMAN resins were used as matrix resin to fabricate BMAN/Silica cloth composites by compression molding process. Heat‐resistant properties of the composites were evaluated by means of dynamic mechanical analysis. The results indicated that thermal resistance of the composites increased as allylation degree of BMAN resins increased. Mechanical properties of the composites, including interlaminar shear strength (ILSS) and flexural strength at room temperature and 300°C, were determined, and the results showed that with increase in allylation degree of matrices the ILSS and flexural strength values of composites at room temperature decreased, but the values of ILSS and flexural strength at 300°C increased. Scanning electron microscope morphology analysis of fracture surface for composites revealed that tough interphase was responsible for the better mechanical properties of the composites based on lower allylation degree resins. POLYM. COMPOS., 28:180–185, 2007. © 2007 Society of Plastics Engineers     

Thermal and dielectric properties of bismaleimide‐triazine resins containing octa(maleimidophenyl)silsesquioxane

Octa(maleimidophenyl)silsesquioxane (OMPS) was synthesized, characterized, and employed to modify the BT resin which composed of 4,4′‐bismaleimidodiphenylmethane (BMI) and 2,2′‐bis(4‐cyanatophenyl)propane (BCE). The curing reaction between OMPS and BT resin was first investigated. It was found that OMPS accelerate the curing reaction of BCE, and the onset temperature of the cyclotrimerization was reduced up to 95.5°C (by DSC). As demonstrated by DSC and FTIR, there was no evidence that indicated the coreaction between maleimide and cyanate ester. 2,2′‐diallyl bisphenol A (DBA) and diglycidyl ether of bisphenol A (E‐51) (Wuxi Resin Factory, Jiangsu Province, China) were also used to enhance the toughness of BT resin, and the formulated BTA (containing DBA) and BTE (containing E‐51) resins were obtained. The thermal properties of BT, BTA, and BTE resins incorporated with OMPS were then investigated. The results of DMA and TG showed that the BT, BTA, and BTE resins containing 1 wt % of OMPS exhibit enhanced thermal properties in comparison with their pristine resins respectively, while more contents of OMPS may impair the thermal properties of the polymer matrix, though the effect of OMPS was slight. Finally, the dielectric constant of these hybrid materials were detected, and their dielectric constant were distinctly reduced by the incorporation of OMPS, while overmuch contents of OMPS were disadvantageous for dielectric constant because of the aggregation of OMPS. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Modification of three‐component bismaleimide resin by poly(phthaloyl diphenyl ether) and related copolymers

A three‐component bismaleimide resin, composed of 4,4′‐bismaleimidodiphenyl methane (BDM), o,o′‐diallyl bisphenol A (DBA), and o,o′‐dimethallyl bisphenol A (1.0/0.3/0.7 eq ratio) was used as a parent bismaleimide resin. Modification of the three‐component bismaleimide resin was examined by blending it with poly(ether ketone ketone)s. Poly(ether ketone ketone)s include poly(phthaloyl diphenyl ether) (PPDE), poly(phthaloyl diphenyl ether‐co‐isophthaloyl diphenyl ether) (PPIDE), and poly(phthaloyl diphenyl ether‐co‐terephthaloyl diphenyl ether) (PPTDE). The PPIDE (51 mol % isophthaloyl) and PPTDE (44 mol % terephthaloyl) were more effective as modifiers for the bismaleimide resin than was PPDE. For example, the fracture toughness (K_IC) for the modified resin increased 30% with no deterioration in the flexural strength and modulus with a 15 wt % inclusion of PPTDE (MW 23,400) compared to the parent three‐component bismaleimide resin: the K_IC increased 95% compared to the value for the Matrimid 5292 resin composed of BDM and DBA. The morphologies of the modified resins changed from particulate to cocontinuous phase structures, depending on the modifier structure and concentration. Toughening of the cured bismaleimide resin could be achieved because of the cocontinuous phase structure. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2991–3000, 2001     

Reaction kinetics and thermal properties of epoxidised cresol novolac/4,4′‐diglycidyl (3,3′,5,5′‐tetramethylbiphenyl) epoxy resin composite cured with aromatic diamine

A series of novel composites based on different ratios of epoxidised cresol novolac (ECN) and 4,4′‐diglycidyl(3,3′,5,5′‐tetramethylbiphenyl) epoxy resin (TMBP) have been prepared with the curing agent 4,4′‐methylenediamine (DDM) and 4,4′‐diaminodiphenylsulfone (DDS), respectively. The investigation of cure kinetics was performed by differential scanning calorimetry using an isoconversional method. The high thermal stabilities of the cured samples were also studied by thermogravimetric analysis. In addition, no phase separation was observed for cured ECN/DDM and ECN/DDS blending with different amounts of TMBP by dynamic mechanical analysis and scanning electron microscopy. Moreover, the cured systems also exhibited excellent impact properties and low moisture absorption. All the results indicate that the ECN/TMBP/DDM and ECN/TMBP/DDS systems are promising materials in electronic packaging. Copyright © 2011 Society of Chemical Industry     

Flame retardancy and dielectric properties of dicyclopentadiene‐based benzoxazine cured with a phosphorus‐containing phenolic resin

A dicyclopentadiene‐based benzoxazine (DCPDBZ) was prepared and separately copolymerized with melamine–phenol formaldehyde novolac or phosphorus‐containing phenolic resin (phosphorus‐containing diphenol) at various molar ratios. Their curing behaviors were characterized by differential scanning calorimetry. The electrical properties of the cured resins were studied with a dielectric analyzer. The glass‐transition temperatures were measured by dynamic mechanical analysis. The thermal stability and flame retardancy were determined by thermogravimetric analysis and a UL‐94 vertical test. These data were compared with those of bisphenol A benzoxazine and 4,4′‐biphenol benzoxazine systems. The effects of the diphenol structure and cured composition on the dielectric properties, moisture resistance, glass‐transition temperature, thermal stability, and flame retardancy are discussed. The DCPDBZ copolymerized with phosphorus‐containing novolac exhibited better dielectric properties, moisture resistance, and flame retardancy than those of the melamine‐modified system. The flame retardancy of the cured benzoxazine/phosphorus‐containing phenolic resins increased with increasing phosphorus content. The results indicate that the bisphenol A and 4,4′‐biphenol systems with a phosphorus content of about 0.6% and the dicyclopentadiene system with a phosphorus content of about 0.8% could achieve a flame‐retardancy rating of UL‐94 V‐0. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of novel phosphorous‐containing biphenol, 2‐(5, 5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorin‐6‐yl)‐1,4‐benzenediol and its application as flame‐retardant in epoxy resin

A novel phosphorous‐containing biphenol, 2‐(5,5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorin‐6‐yl)‐ 1,4‐benzenediol (DPODB), was prepared by the addition reaction between 5,5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorinane phosphonate (DPODP) and p‐benzoquinone (BQ). The compound (DPODB) was used as a reactive flame retardant in o‐cresol formaldehyde novolac epoxy resin (CNE) for electronic application. The structure of DPODB was confirmed by FTIR and NMR spectra. Thermal properties of cured epoxy resin were studied using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The flame retardancy of cured epoxy resins was tested by UL‐94 vertical test and achieved UL‐94 vertical tests of V‐0 grade (nonflammable). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3842–3847, 2006     

Thermal characterization of carbon‐nanofiber‐reinforced tetraglycidyl‐4,4′‐diaminodiphenylmethane/4,4′‐diaminodiphenylsulfone epoxy composites

The thermal properties of carbon nanofibers (CNF)/epoxy composites, composed of tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM) resin and 4,4′‐diaminodiphenylsulfone (DDS) as a curing agent, were investigated with differential scanning calorimetry (DSC), thermogravimetric analysis, and dynamic mechanical thermal analysis. DSC results showed that the presence of CNF had no pronounced influence on the heat of the cure reaction. However, the incorporation of CNF slightly improved the thermal stability of the epoxy. Furthermore, the storage modulus of the TGDDM/DDS epoxy was significantly enhanced, whereas the glass‐transition temperature was not significantly affected, upon the incorporation of CNFs. The storage modulus of 5 wt % CNF/epoxy composites at 25°C was increased by 35% in comparison with that of the pure epoxy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 295–298, 2006     

Flexible epoxy novolac coatings: Use of cardanol‐based flexibilizers

Flexible epoxy novolac coatings were developed by reacting an epoxy novolac resin, poly[(phenylglycidyl ether)‐co‐formaldehyde] (PPGEF) with an amine curing agent, 4,4′‐diamino‐3,3′‐dimethyldicyclohexyl methane (BMCHA), cardanol based reactive diluent (Cardolite NC‐513) and two different cardanol‐based flexibilizers (Cardolite NC‐514 and Cardolite NC‐547). The flexibilizer content was varied from 5 to 10% by weight of the resin. These resins were coated onto the stainless steel panels and tested for their gloss, cross‐hatch adhesion, falling weight impact resistance, flexibility, abrasion, scratch hardness, solvent scrub resistance, and chemical resistance. The thermo‐mechanical properties of these coatings were determined by TGA, DSC, DMTA, and tensile strength measurements. The cryofractured specimens were subjected to SEM analysis. The influence of structural differences of two flexibilizers on the coating properties was investigated. These coatings exhibited excellent properties and have great potential in industrial applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44920.