Novel modified bismaleimide resins with improved ablativity

To improve the ablativity of bismaleimide-type resins, a series of novel allyl compounds containing boron in their molecular structure, designated as ACB, were synthesized and characterized. The copolymers made up of 4,4′-bismaleimidodiphenyl methane (BDM) and each ACB were prepared. The properties of the prepolymers and cured resins were all studied in detail. Results show that the prepolymers of BDM/ACB systems have similar processing characteristics such as solubility in acetone and reactivity to those of ordinary BMI resins made up of BDM and allyl compounds without boron, such as the famous BDM/BA (O,O′-diallylbisphenol A) system, while the thermal resistance and ablativity of the former are better than those of the latter. Thermogravimetric analysis (TGA) in a nitrogen atmosphere revealed that the BDM/ACB systems were stable up to 480°C and their char yields at 800°C under anaerobic conditions were more than 50%. However, the char yield at 700°C of the BDM/BA system is only about 21%. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1623–1631, 1999     

High performance self‐healing bismaleimide/diallylbisphenol a/poly(phenylene oxide) microcapsules composites with low temperature processability

Novel high performance self‐healing 4,4′‐bismaleimidodiphenylmethane (BDM)/diallylbisphenol A(BA)/poly(phenylene oxide) microcapsules filled with epoxy resin (PPOMCs) systems with low temperature processability were developed. The effects of PPOMCs on the reactivity of BDM/BA resin system were investigated; the properties of cured BDM/BA/PPOMCs systems such as fracture toughness, dynamic mechanical property, dielectric property, and self‐healing ability were discussed. The morphologies of the cured resin systems were characterized using scanning electronic microscope and light microscopy. Results reveal that the addition of PPOMCs can catalyze the polymerization reaction of BDM/BA resins. BDM/BA systems with appropriate PPOMCs content cured at low temperature possess excellent fracture toughness, high glass transition temperature (T_g), and low dielectric property. The self‐healing ability of BDM/BA can be realized by the introduction of PPOMCs owing to the polymerization of the released core materials from PPOMCs. The self‐healing efficiency of healed BDM/BA/PPOMCs systems can be influenced by the size and content of PPOMCs and the contact areas between the crack surfaces. © 2013 Society of Plastics Engineers     

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     

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.     

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.     

BMI Based Composites With Low Dielectric Loss

Summary O,O’-diallylbisphenol A (BA), allyl epoxy resins and epoxy acrylate resins are adopted to copolymerize with 4,4’-bismaleimidodiphenyl methane (BDM) resins and modify mechanical properties and processing charicteristics. The new modified BMI resin 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. Composites based on modified BMI resins and reinforced by glass fibre and quartz fibre possess excellent mechanical properties. The fracture surfaces of the composites are examined by scanning electron microscopy (SEM). It is indicted that modified BMI resin matrix composites put up typical toughness rupture and the adhesion efficiency in interface of composites is fine. When the test frequency scope is from 1 GHz to 20 GHz, the dielectric constant and dielectric loss of composites almost hold the line. After 100 h in boil water, mechanical and dielectric properties of composites are higher than 85% retention of their original values.     

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.     

Fatty acid‐based comonomers as styrene replacements in soybean and castor oil‐based thermosetting polymers

In this study, a fatty acid‐based comonomer is employed as a styrene replacement for the production of triglyceride‐based thermosetting resins. Styrene is a hazardous pollutant and a volatile organic compound. Given their low volatility, fatty acid monomers, such as methacrylated lauric acid (MLA), are attractive alternatives in reducing or eliminating styrene usage. Different triglyceride‐derived cross‐linkers resins were produced for this purpose: acrylated epoxidized soybean oil (AESO), maleinated AESO (MAESO), maleinated soybean oil monoglyceride (SOMG/MA) and maleinated castor oil monoglyceride (COMG/MA). The mechanical properties of the bio‐based polymers and the viscosities of bio‐based resins were analyzed. The viscosities of the resins using MLA were higher than that of resins with styrene. Decreasing the content of MLA increased the glass transition temperature (T_g). In fact, the T_g of bio‐based resin/MLA polymers were on the order of 60°C, which was significantly lower than the bio‐based resin/styrene polymers. Ternary blends of SOMG/MA and COMG/MA with MLA and styrene improved the mechanical properties and reduced the resin viscosity to acceptable values. Lastly, butyrated kraft lignin was incorporated into the bio‐based resins, ultimately leading to improved mechanical properties of this thermoset but with unacceptable increases in viscosity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modification of two-component bismaleimide resin by blending (meth)allyl compounds as third components

A two-component bismaleimide resin composed of 4,4′-bismaleimidediphenyl methane (BDM) and o,o′-diallyl bisphenol A (DBA) (Matrimid 5292 resin) was used as a parent bismaleimide resin. Modification of the parent bismaleimide resin was examined using several kinds of (meth)allyl compounds as the third component. The (meth)allyl compounds include triallyl isocyanurate (TAIC), o,o′-dimethallyl bisphenol A (DMBA) and trimethallyl isocyanurate (TMAIC). In the ternary BDM/DBA/TAIC blends, the fracture toughness K_IC and flexural strength for the cured resins decreased with increasing TAIC content; thermal properties of the cured resins were not deteriorated. In the ternary BDM/DBA/DMBA blends, K_IC and flexural modulus for the cured resins increased and their glass transition temperatures decreased with an increase in DMBA content. Flexural strength increased up to DMBA 70 eq% blend and then decreased. In the ternary blend of BDM/DBA/TMAIC (1.0/0.5/0.5), K_IC for the blend increased 15%, with retention of flexural property and T_g. In the ternary BDM/DMBA/TMAIC (1.0/0.5/0.5) blend, the cured resin had balanced properties and its K_IC increased 50% compared to the cured Matrimid resin. © 1999 Society of Chemical Industry     

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.     

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     

Synthesis and characterization of bio‐based thermosetting resins from lactic acid and glycerol

A bio‐based thermoset resin has been synthesized from glycerol reacted with lactic acid oligomers of three different chain lengths (n): 3, 7, and 10. Lactic acid was first reacted with glycerol by direct condensation and the resulting branched molecule was then end‐functionalized with methacrylic anhydride. The resins were characterized by Fourier‐transform infrared spectroscopy (FT‐IR), by ¹³C‐NMR spectroscopy to confirm the chemical structure of the resin, and by differential scanning calorimetry and dynamic mechanical thermal analysis (DMTA) to obtain the thermal properties. The resin flow viscosities were also measured using a rheometer with different stress levels for each temperature used, as this is an important characteristic of resins that are intended to be used as a matrix in composite applications. The resin with a chain length of three had better mechanical, thermal, and rheological properties than the resins with chain lengths of seven and 10. Also, its bio‐based content of 78% and glass transition temperature of 97°C makes this resin comparable to commercial unsaturated polyester resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40488.     

Chemically stable polyphenylene ether microcapsules prepared using a facile method for the self‐healing of polymers

Chemically stable polyphenylene ether (PPO) microcapsules (MCs) filled with epoxy resins (PPO‐EP MCs) were prepared using low‐molecular‐weight PPO with vinyl end‐groups as shell wall and epoxy resins as core material using an oil‐in‐water emulsion solvent evaporation method. This method for synthesizing MCs with PPO shell walls is simple, convenient and novel, which can avoid the influence of processing parameters on the chemical stability of the epoxy resin core material. The resulting PPO‐EP MCs exhibit good chemical stability below 255 °C mainly owing to the absence of a polymerization catalyst of the epoxy resins. The initial thermal decomposition temperature of the MCs is about 275 °C. The MCs were embedded in a 4,4′‐bismaleimidodiphenylmethane/O,O′‐diallylbisphenol A (BMI/BA) thermosetting resin system. When processed at high temperature (up to 220 °C), the microencapsulated epoxy resins could be released from the fractured MCs to matrix crack surfaces and bond the crack surfaces. An amount of 8 wt% MCs restored 91 and 112% of the original fracture toughness of the BMI/BA matrix when heated at 220 °C/2 h and 80 °C/1 h + 220 °C/2 h, respectively. The MCs only slightly decreased the thermal property of the matrix. © 2016 Society of Chemical Industry     

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     

Use of allyl‐functional benzoxazine monomers as replacement for styrene in vinyl ester resins

New vinyl ester systems are prepared using allyl‐functional benzoxazine monomers, 3‐allyl‐6‐methyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazine (pC‐ala) or bis(3‐allyl‐3,4‐dihydro‐2H‐benzo[e][1,3]oxazin‐6‐yl)methane (BF‐ala), as reactive diluents for vinyl ester resins derived from an epoxy resin, diglycidyl ether of bisphenol A, instead of using styrene. Different initiators are used to investigate the copolymerization of allyl function from pC‐ala with vinyl function from vinyl ester resin prepolymer. The temperature dependence of viscosity is studied to demonstrate the retention of processability of the new vinyl ester resins. Dynamic mechanical and thermogravimetric analyses are used to investigate the dynamic mechanical properties and thermal stability of the new resins. Copyright © 2012 Society of Chemical Industry     

Preparation and characterization of soluble bismaleimide‐triazine resins based on asymmetric bismaleimide

A series of bismaleimide‐triazine resins (EBT) were prepared from 2‐(4′‐maleimido)phenyl‐2‐(4′‐maleimidophenoxyl)phenylbutane (EBA‐BMI) and 2,2‐bis(4‐cyanatophenyl)propane (BADCy). The resins show attractive processability with good solubility in low boiling point solvents and wide processing temperature windows. Introduction of diallylbisphenol A (DBA) can decrease the curing temperature of EBT resins that the curing exothermic peak temperature shifted from 291 to 237 °C as the content of DBA increased from 0 to 20%. The curing condition influenced the thermal properties of the cured EBT resins. The glass transition temperature increased as the curing temperature and curing time increased. The cured EBT resins show high glass transition temperature up to 352 °C, high thermal stability with 5% weight loss temperature over 405 °C, low coefficient of thermal expansion about 45 to 52 ppm/°C, and high storage modulus up to 2.6 GPa at 250 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44519.     

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     

Research progress on bio‐based thermosetting resins

Compared with the rapid progress on bio‐based thermoplastics, research on bio‐based thermosetting resins should have attracted much more attention, considering that they will have a bright future. In this paper, the current research progress on bio‐based thermosetting resins is reviewed. We pay special attention to the synthesis and investigation of properties of epoxies and unsaturated polyesters derived from renewable plant oil, cardanol, rosin acid, lignin, glycerol, gallic acid, furan, isosorbide, itaconic acid, etc. This mini review gives an overall perspective for bio‐based thermosets.© 2015 Society of Chemical Industry     

Investigation of the curing mechanism and properties of bismaleimide-triazine resins containing phenolphthalein and cyano group

A series of bismaleimide-triazine (BT) resins with and without O, O′-diallyl bisphenol A (DABPA) were produced by mixing 2, 2-bis (4-cyanatophenyl) propane (BADCy) and MCBMI (2,6-bis(4-(1-(4-(4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)phenoxy)-3-methylphenyl)-3-oxo-1,3-dihydroisobenzofuran-1-yl)-2-methylphenoxy)benzonitrile). The resins show just one glass-transition temperature (T _g) and enhanced flexural properties as well as superior fracture toughness compared with commercial BDM/BADCy system, in which BDM is (N,N′-bismaleimido-4,4′-diphenylmethane). Introduction of DABPA can decrease the curing temperature of bismaleimide-triazine (BT) resins but increase its impact strength. When the mole of DABPA reach up to 1.2, the impact strength was increased by 1.34 times in comparison with BDM/ BADCy system. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 136, 47420.     

Modification of bismaleimide with allyl compound and N‐phenylmaleimide

Three different formulas with low‐cost resins, made up of N,N′‐bismaleimidephenylmethane (BMI), O,O′‐diallybisphenol A(BA), and N‐phenylmaleimide (NPMI) were developed. The properties of prepolymers, such as activation energies, enthalpy, and constants of reaction rate, were obtained by a kinetic programmer on DSC. Thermal and mechanical properties of neat resins were also studied. The results showed that the systems had low melting point and low viscosity. All cured resins presented excellent thermal and good mechanical properties. The mechanical properties could be affected by the quantity of NPMI and postcuring process. The water absorption is ≤1.98%; heat deflection temperature (HDT) is ≥250°C after aging for 100 h in distilled water of 90°C. The data indicate that the BMI can be effectively improved by adding BA and NPMI, while its heat resistance and hot/wet mechanical properties can be fairly retained. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2518–2522, 2001