Studies of phosphonate‐containing bismaleimide resins. I. Synthesis and characteristics of model compounds and polyaspartimides

Two phosphonate‐containing bismaleimide (BMI) [(4,4′‐bismaleimidophenyl)phosphonate] monomers with different melting temperatures and similar curing temperatures were synthesized by reacting N‐hydroxyphenylmaleimide with two kinds of dichloride‐terminated phosphonic monomers. The BMI monomers synthesized were identified with ¹H‐, ¹³C‐, and ³¹P‐nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. The phosphonate‐containing BMI monomers react with a free‐radical initiator to prepare phosphonate‐containing BMI polymers and also with various aromatic diamines to prepare a series of polyaspartimides as reactive flame retardants. The polymerization degrees of polyaspartimides depend on the alkalinity and nucleophility of diamines as chain extenders. Differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA) were used to study the thermal properties of the phosphonate‐containing BMI resins such as the melting temperature, curing temperature, glass transition temperature (T_g), and thermal resistance. All the phosphonate‐containing BMI resins, except the BMI polymers, have a T_g in the range of 210–256°C and show 5% weight loss temperatures (T_5%) of 329–434 and 310–388°C in air and nitrogen atmospheres, respectively. The higher heat resistance of cured BMI resin relative to the BMI polymer is due to its higher crosslinking density. Since the recrosslinking reactions of BMI polymers and polyaspartimides occur more easily in an oxidation environment, their thermal stabilities in air are higher than are those in nitrogen gas. In addition, the thermal decomposition properties of polyaspartimides depend on the structures and compositions of both the diamine segments and the BMI segments. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1919–1933, 2002     

Synthesis and properties of trifluoromethyl groups containing epoxy resins cured with amine for low Dk materials

The study synthesized a trifluoromethyl (CF₃) groups with a modified epoxy resin, diglycidyl ether of bisphenol F (DGEBF), using environmental friendly methods. The epoxy resin was cured with 4,4′‐diaminodiphenyl‐methane (DDM). For comparison, this study also investigated curing of commercially available diglycidyl ether of bisphenol A (DGEBA) with the same curing agent by varying the ratios of DGEBF. The structure and physical properties of the epoxy resins were characterized to investigate the effect of injecting fluorinated groups into epoxy resin structures. Regarding the thermal behaviors of the specimens, the glass transition temperatures (T_g) of 50–160°C and the thermal decomposition temperatures of 200–350 °C at 5% weight loss (T_d5%) in nitrogen decreased as amount of DGEBF increased. The different ratios of cured epoxy resins showed reduced dielectric constants (D_k) (2.03–3.80 at 1 MHz) that were lower than those of pure DGEBA epoxy resins. Reduced dielectric constant is related to high electrronegativity and large free volume of fluorine atoms. In the presence of hydrophobic CF₃ groups, the epoxy resins exhibited low moisture absorption and higher contact angles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis,curing behavior and thermal properties of silicon‐containing hybrid polymers with Si−C≡C units

Three novel kinds of linear silicon‐containing hybrid polymers with Si?C≡C units were synthesized by polycondensation reactions using the Grignard reagent method. All the polymers were thermosetting, highly heat‐resistant, moldable and easily soluble in common organic solvents. The structure, curing behavior, thermal and oxidative properties were characterized using Fourier transform infrared spectroscopy, ¹H NMR, ¹³C NMR, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. The results obtained can provide theoretical guidance for determining the curing of the resin system. In addition, the cured polymers exhibit excellent thermal and oxidative stabilities with temperatures of 5% weight loss (T_d5) above 480 °C and 450 °C in nitrogen and air respectively; the residues at 1000 °C were above 70.0% and 45.0% respectively. The thermal and oxidative stabilities of the polymers are attributed to a crosslinking reaction between the Si?H and C≡C bonds or C≡C bonds. These polymers have the potential for use as high‐temperature‐resistant resins and ceramic precursors. © 2013 Society of Chemical Industry     

Novel propargylether‐terminated monomers containing pyridine and phenyl pendent group: Synthesis,cure, and properties

Two novel propargylether‐terminated resins containing pyridine and bulky phenyl pendent group were prepared from propargyl bromide and different diphenols, and highly thermal stable polymers were obtained by the thermal cure of the monomers. The chemical structures of these novel monomers were well confirmed by FTIR, ¹H‐NMR and elemental analysis. Curing and thermal behavior of the resins were investigated using differential scanning calorimetry (DSC) and dynamic thermogravimetry in argon atmosphere. DSC curves of these two monomers showed a single endothermic peak corresponding to the conformation of chromene ring and homopolymerization of the chromene ring. The temperature at 5% weight loss (T_d5) was higher than 440°C under argon and the highest glass transition temperature (T_g) reached 362°C. The rheological behavior and solubility of the monomer were also investigated. The monomers showed excellent flow‐ability, broad processing window, and great solubility. These results showed that the two resins could be ideal candidates for high‐temperature resistant resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40469.     

Preparation and thermal properties of bismaleimide blends based on hydroxyphenyl maleimide

N‐(4‐hydroxyphenyl)maleimide was melt‐blended with the glycidyl ether of bisphenol‐A and various mole percentages of 4, 4′‐(diaminodiphenylsulfone) bismaleimide. The cure behaviour of the resins was evaluated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The blends showed distinct reductions in the onset of cure (T_o) and peak exothermic (T_exo) temperatures. The blends cured at low temperatures exhibited glass transition temperatures (T_gs) higher than the cure temperatures. The cured blends showed high moduli, glass transition temperatures in excess of 250 °C and good thermal stabilities up to 400 °C. Copyright © 2005 Society of Chemical Industry     

Catalytic effect of 2,2′‐diallyl bisphenol A on thermal curing of cyanate esters

Cyanate esters are a class of thermal resistant polymers widely used as thermal resistant and electrical insulating materials for electric devices and structural composite applications. In this article, the effect of 2,2′‐diallyl bisphenol A (DBA) on catalyzing the thermal curing of cyanate ester resins was studied. The curing behavior, thermal resistance, and thermal mechanical properties of these DBA catalyzed cyanate ester resins were characterized. The results show that DBA is especially suitable for catalyzing the polymerization of the novolac cyanate ester resin (HF‐5), as it acts as both the curing catalyst through depressing the exothermic peak temperature (T_exo) by nearly 100°C and the toughening agent of the novolac cyanate ester resin by slightly reducing the elastic modulus at the glassy state. The thermogravimetric analysis and dynamic mechanical thermal analysis show that the 5 wt % DBA‐catalyzed novolac cyanate ester resin exhibits good thermal resistance with T_d⁵ of 410°C and the char yield at 900°C of 58% and can retain its mechanical strength up to 250°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1775–1786, 2006     

High glass transition temperature bismaleimide‐triazine resins based on soluble amorphous bismaleimide monomer

A novel bismaleimide (DOPO‐BMI) with unsymmetrical chemical structure and DOPO pendant group has been prepared. The particular molecular structure makes DOPO‐BMI show an intrinsic amorphous state with a T_g about 135°C and excellent solubility in most organic solvents, which is beneficial to the processability of bismaleimide composite materials. A series of bismaleimide‐triazine (BT) resins have been prepared based on DOPO‐BMI and 2,2‐bis(4‐cyanatophenyl)propane at various weight ratios. The prepared BT resins show outstanding solubility in organic solvent and low viscosity about 10–671 mPa s at 180°C. The cured BT resins exhibit high glass transition temperature (T_g) over 316°C. As the weight ratio of DOPO‐BMI increases to 80% (BT80), the T_g can rise to 369°C (tan δ). The cured BT resins also show good thermal stability with the 5% weight loss temperature over 400°C under both nitrogen and air atmosphere. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42882.     

Synthesis and properties of methyl hexahydrophthalic anhydride‐cured fluorinated epoxy resin 2,2‐bisphenol hexafluoropropane diglycidyl ether

The fluorinated epoxy resin, 2,2‐bisphenol hexafluoropropane diglycidyl ether (DGEBHF) was synthesized through a two‐step procedure, and the chemical structure was confirmed by ¹H n uclear magnetic resonance (NMR), ¹³C NMR, and Fourier transform infrared (FTIR) spectra. Moreover, DGEBHF was thermally cured with methyl hexahydrophthalic anhydride (MHHPA). The results clearly indicated that the cured DGEBHF/MHHPA exhibited higher glass transition temperature (T_g 147°C) and thermal decomposition temperature at 5% weight loss (T₅ 372°C) than those (T_g 131.2°C; T₅ 362°C) of diglycidyl ether of bisphenol A (DGEBA)/MHHPA. In addition, the incorporation of bis‐trifluoromethyl groups led to enhanced dielectric properties with lower dielectric constant (D_k 2.93) of DGEBHF/MHHPA compared with cured DGEBA resins (D_k 3.25). The cured fluorinated epoxy resin also gave lower water absorption measured in two methods relative to its nonfluorinated counterparts. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2801–2808, 2013     

Synthesis and properties of side chain cholesteric liquid‐crystalline polyacrylates containing two mesogenic groups

The synthesis of side chain cholesteric liquid‐crystalline polymers containing both 4‐cholesteryl‐4'‐acryloyloxybenzoate (M_I) and 4‐methoxyphenyl‐4'‐acryloyloxybenzoate (M_II) mesogenic side groups is described. The chemical structures of the obtained monomers and polymers are confirmed by Fourier transform infrared (FTIR) spectroscopy. The phase behavior and optical properties of the synthesized monomers and polymers were investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), and thermogravimetric analyses (TGA). The homopolymer IP reveals a cholesteric phase and VIIP displays a nematic phase. The copolymers IIP–VIP exhibit, respectively, cholesteric oily‐streak texture and focal‐conic texture. The fixation of the helical pitch and oily‐streak texture of the cholesteric phase is achieved by quenching, and polymer films with different reflection colors are obtained. The experimental results demonstrate that the glass transition temperature (T_g) and the melting temperature (T_m) of the copolymers IIP–VIP decrease, whereas the isotropization temperature (T_i) and the mesomorphic temperature range (ΔT) increase with increasing content of mesogenic M_II units. TGA results indicate that the temperatures at which 5% mass loss occurred (T_5wt%) of all copolymers are >245°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1936–1941, 2003     

Synthesis and properties of fluorinated bis‐benzocyclobutene‐terminated arylene ether monomers

Four novel bis‐benzocyclobutene‐endcapped arylene ether monomers, 1,1′‐bis[4‐(4′‐benzocyclobutenyloxy)phenyl]‐1‐phenyl‐2,2,2‐trifluoroethane (BOPP3FE), 1,1′‐bis[4‐(4′‐benzocyclobutenyloxy)phenyl]‐1‐(3′,5′‐ditrifluoromethyl)phenyl‐2,2,2‐trifluoroethane(BOPP9FE), 2,2′‐bis[4‐(4′‐benzocyclobutenyloxy)phenyl]‐1,1,1,3,3,3‐hexfluoropropane (BOP6FP), and 2,2′‐bis[4‐(4′‐benzocyclobutenyloxy)phenyl]‐propane (BOPP) were prepared and characterized. All the four monomers showed similar curing behaviors under N₂ (Differential scanning calorimetry: extrapolated onset and peak temperatures at 225–229°C and 261–263°C) and demonstrated low and steady melt viscosities between 110 and 200°C, indicating their good processability. After cure, the resulting BCB resins exhibited high T_g (232–282°C) and excellent thermal stability (T_5% > 433°C). The resins also showed good mechanical properties with the flexural strengths of 68–88 MPa and the flexural modulus of 2.52–3.15 GPa. Moreover, the resins also exhibited low dielectric constants (2.58–2.88), low dissipation factors (2.7 to 8.4 × 10?4) and low water absorptions in boiling water for 24 h (0.29–0.59%). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

One‐pot synthesis of hyperbranched poly(aryl ether ketone)s for the modification of bismaleimide resins

Hyperbranched poly(aryl ether ketone)s with hydroxyl end groups (HBP‐OH) and high degree of branching value (83%) were synthesized via an A₂ + B₃ approach. The polymerization conditions (e.g., polymerization temperature and time, monomer concentration, stoichiometric ratio of functional groups) were explored to avoid the gelation. Allyl‐terminated hyperbranched PAEKs (HBP‐AL) with low molecular weight (M_n = 3.4 × 10³) and narrow polydispersity (PDI = 1.65) were obtained via the etherification of HBP‐OH and it has been used for the modification of bismaleimide (BMI) resins. The prepolymers showed good processibilities with a viscosity below 0.6 Pa s at 110°C, though the viscosities slightly increased as the increase of HBP‐AL contents. The cured BMI resins showed high glass transition temperatures (T_g > 320°C) and good thermal stabilities (T_d > 400°C, both in nitrogen and air). It is inspiring to note that the incorporation of HBP‐AL into BMI matrix results in a significant enhancement of toughness without any noticeable loss in modulus, processibility, and T_g. POLYM. ENG. SCI., 54:1675–1685, 2014. © 2013 Society of Plastics Engineers     

Synthesis of a novel series of propargyloxyphenyl maleimides and their characterization as thermal‐resistance resins

Novel thermosetting monomers possessing both maleimide and propargyl groups were first designed and synthesized. The monomers included N‐(2‐propargyloxyphenyl) maleimide (2‐PPM), N‐(3‐propargyloxyphenyl) maleimide (3‐PPM), and N‐(4‐propargyloxyphenyl) maleimide (4‐PPM), and their structures were confirmed with Fourier transform infrared (FTIR) spectroscopy, ¹H‐NMR, and elemental analysis. The cure behaviors of these monomers were characterized with differential scanning calorimetry and FTIR spectroscopy, and the results indicated that the monomers had a broader processing window than normal bismaleimide (BMI) resins. The thermal properties of the cured monomers were characterized with thermogravimetric analysis and dynamic mechanical analysis. The 5% mass loss temperatures of the cured monomers were high (ca. 400°C), and the glass‐transition temperatures of cured 2‐PPM, 3‐PPM, and 4‐PPM were 386, 373, and 387°C, respectively, which were much higher than those of typical commercial blended BMI resins. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of the two novel liquid crystalline epoxy resins based on bisphenol‐s mesogen

Two novel liquid crystalline epoxy resins (LCER) based on bisphenol‐S mesogen, 4,4′‐Bis‐(2,3‐epoxypropyloxy)‐sulfonyl bis(1,4‐phenylene) (p‐BEPSBP) and sulfonyl bis(4,1‐phenylene) bis[4‐(2,3‐epoxypropyloxy)benzoate] (p‐SBPEPB), were synthesized. Their liquid crystalline behavior and structure were characterized by Fourier transmittance infrared ray (FTIR), differential scanning calorimetry (DSC), ¹HNMR, polarized optical microscopy (POM) and X‐ray diffraction (XRD). The results show that p‐BEPSBP is a kind of thermotropic liquid crystal and has a smectic mesophase with a melting point (T_m) at 165°C; the p‐SBPEPB is a kind of nematic mesophase with the temperature range of 155–302°C from the T_m to the clearing point T_i. The curing behaviors and texture of the liquid crystalline epoxy resins with 4,4′‐diaminodiphenyl ether (DDE) were also studied by DSC and some kinetic parameters were evaluated according to the Ozawa's method. The dynamic mechanical properties of curing products were also investigated by torsional braid analysis (TBA), and the results suggest that the dynamic mechanical loss peak temperature (T_p) of p‐BEPSBP/DDE and p‐SBPEPB/DDE is 120 and 130°C, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Bismaleimides,bisnadimides, and polyaspartimides containing ether and ester linkages and pyridine

A series of bismaleimides (BMI) and bisnadimides (BNI) containing pyridine ring and flexible linkages were prepared and the structural characterization of the resins was carried out by elemental analysis, FTIR, ¹H NMR, and ¹³C NMR spectroscopy. Their curing behavior were characterized by differential scanning calorimetry and thermal stability of the cured resins were investigated by thermogravimetric analysis. In addition, a series of polyaspartimides were prepared by the polyaddition of the bismalemide with various dimaines. The polymers were characterized by FT‐IR, inherent viscosity, and molecular weight measurements. All the polyimides were soluble in many organic solvents, the glass transition temperature of the polyaspartimides are in the range of 194–231°C, 10% weight loss (T₁₀) takes place in the temperature range of 379–482°C in N₂ and char yield in the range of 44.31–53.31%. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Europium‐containing cholesteric liquid crystalline polymers in the side chain

Europium‐containing cholesteric liquid crystalline polymers were graft copolymerized using poly(methylhydrogeno)siloxane, cholesteryl 4‐(allyloxy)benzoate (M₁), cholesteryl acrylate (M₂), and a europium complexes monomer (M₃). The chemical structures of the monomers were characterized by Fourier transform infrared and ¹H‐nuclear magnetic resonance. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, thermo gravimetric analysis, polarizing optical microscopy, and X‐ray diffraction. With an increase of europium complexes units in the polymers, the glass transition temperature (T_g) did not change significantly; the isotropic temperature (T_i) and mesophase temperature range (ΔT) decreased. All polymers showed typical cholesteric Grandjean textures, which was confirmed by X‐ray diffraction. The temperatures at which 5% weight loss occurred (T_d) were greater than 300°C for the polymers. The introduction of europium complexes units did not change the liquid crystalline state of polymer systems; on the contrary, the polymers were enabled with the significant luminescent properties. With Eu³⁺ ion contents ranging between 0 and 1.5 mol %, luminescent intensity of polymers gradually increased and luminescent lifetimes were longer than 0.45 ms for the polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40866.     

Trifunctional quinoxaline-based maleimide and its polymer alloys with benzoxazine: Synthesis,characterization, and properties

Novel quinoxaline-based trismaleimide (2,3-di[3-maleimido]phenyl-6- maleimidoquinoxaline, namely TQMI) and its polymer alloys with 3-phenyl-3,4-dihydro-2H-1,3-benzoxazine (P-a) were successfully prepared and characterized. Differential scanning calorimetry investigation of TQMI exhibited distinct double exothermic peaks, which implied that the curing behavior of different type of maleimide group was discrepant. The curing temperature of P-a/TQMI prepolymers was lower than that of both neat TQMI and P-a monomer. The temperatures at 5% (T₅) and 10% (T₁₀) weight loss and the char yield (Y_c) of cured TQMI at 800°C reached 513°C, 524°C, and 63.5%, respectively, which were much higher than the record of traditional 4,4′-bismaleimideodiphenylmethane (BMDPM) resin as well as most of other reported bismaleimide resins. Moreover, the addition of TQMI enhanced thermal stability, glass transition temperature (T_g), and limiting oxygen index of benzoxazine resin dramatically. Attractively, the T_g value of P-a/TQMI copolymer at 30 wt% TQMI loadings was approximately 20°C higher than that of P-a/BMDPM copolymer owing to the bulky quinoxaline group.     

Synthesis and properties of silicon-containing bismaleimide resins

Two novel bismaleimide (BMI) monomers containing silicon atom in the structure, i.e., bis[4-(4-maleimidophenylcarbonyloxy)phenyl]dimethylsilane (BMI-SiE1) and bis[4-(4-maleimidophenyloxycarbonyl)phenyl]dimethylsilane (BMI-SiE2), were designed, synthesized, and polymerized with and without the use of diamine as comonomers to yield novel silicon-containing BMI resins. Both monomers obtained are readily soluble in organic solvents, such as chloroform and N, N-dimethylformamide. Differential scanning calorimetry and thermogravimetric analysis investigation of these two monomers indicated a high polymerization temperature (T_p > 240°C) and a good thermal and thermo-oxidative stability of cured BMI resins. The onset temperature for 5% weight loss was found to be above 450°C in nitrogen and above 400°C in the air. Polymerization of BMI-SiE1 and BMI-SiE2 with 4,4′-diaminodiphenylether (DPE) yielded a series of polyaspartimides that had good solubility and could be thermally cured at 250°C. TGA investigations of the cured diamine-modified BMI resins showed onset of degradation temperatures (T_ds) in the range of 344–360°C in nitrogen and 332–360°C in the air. Composites based on the cured diamine-modified BMI resins and glass cloth were prepared and characterized for their dynamic mechanical properties. All the composites showed high glass transition temperatures (e.g., >190°C) and high bending modulus in the range of 1000–2700 MPa. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal behavior and properties of naphthalene containing bismaleimide–triazine resins

A series of bismaleimid·triazine (BT) resins were prepared from various dicyanate esters and 2,7-bis(4-maleimidophenoxy)naphthalene (BMPN), which contains a naphthalene group and an aryl ether linkage in the backbone. Their curing behaviors were characterized by differential scanning calorimetry. The exotherm temperature and polymerization reactivity were strongly affected by the chemical structure of the various dicyanate ester monomer. Thermal behaviors were investigated by thermogravimetric analyses and dynamic mechanical analyses. The glass transition temperatures (T_g) of these cured resins with bismaleimide/dicyanate ester at the 1/2 molar ratio were in the range of 250–322°C, and exhibited excellent thermal stability up to 400°C in nitrogen. These results provided a structure–properties relationship for the cured bismaleimid·triazine resins. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1199–1207, 1998     

Studies on syntheses and properties of episulfide‐type optical resins with high refractive index

A series of novel high refractive index episulfide‐type optical resins were prepared by ring‐opening copolymerization of bis(β‐epithiopropylthioethyl) sulfide (BEPTES) with episulfide derivative of diglydicyl ether of bisphenol A (ESDGEBA) and 2,4‐tolylene diisocyanate (TDI), respectively, in the presence of triethylamine as a curing catalyst. The episulfide monomers, BEPTES and ESDGEBA, were synthesized from their corresponding epoxy compounds, respectively. The cured transparent resins exhibit high refractive index (n_d > 1.63) and relatively low dispersion. The refractive index (n_d) and Abbe's number (ν_d) of the BEPTES/ESDGEBA curing system increased linearly with the weight content of BEPTES monomer in the range from 1.633 and 34.0 for the copolymer with 10 wt % of BEPTES to 1.697 and 38.1 for the homopolymer of pure BEPTES. For the BEPTES/TDI curing system, the refractive index and Abbe's number varied linearly with the molar ratio of BEPTES to TDI from 1.652 and 28.7 to 1.669 and 34.6. High glass‐transition temperatures (T_g > 130°C) of the cured BEPTES/TDI resins were observed, which indicate that the cured BEPTES/TDI resins possess a good heat resistance. The optical, physical, and thermal properties of the episulfide‐type cured optical resins were also discussed in this study. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2426–2430, 2003     

Materials containing benzocyclobutene units with low dielectric constant and good thermostability prepared from star-shaped molecules

With the development of ultralarge-scale integrated circuits, polymers with low dielectric constant and high thermal stability have aroused great interest. We prepared two novel bridged siloxane-based benzocyclobutene (BCB) star-shaped monomers, tetrakis[dimethyl siloxy-4-(1′,1′-dimethyl-1′-ethyl silicon)-benzocyclobutene] (TDSDES-BCB) and tetrakis(hexamethyl siloxane vinyl-benzocyclobutene) (THSV-BCB), and the corresponding resins were obtained by curing. The structures of TDSDES-BCB and THSV-BCB were confirmed by ¹H-NMR, ¹³C-NMR, and ²⁹Si-NMR spectra and time-of-flight mass spectrometry analysis. The curing behavior of these monomers was investigated by Fourier transform infrared spectroscopy and differential scanning calorimetry. The dielectric constant of cured TDSDES-BCB is only 2.43 at 10 MHz (that of THSV-BCB is 2.46). In addition, these resins display high thermal stability: the 5 wt % weight loss temperature of cured TDSDES-BCB is about 467 °C (454 °C for THSV-BCB resin). The excellent low dielectric property is attributable to the free volume created by the star-shaped structure and crosslinked network structure of BCB after curing. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47458.