Herein, the catalytic effects of aromatic amines with different structures on the room temperature curing of bisphenol E cyanate (BECy) have been studied using differential scanning calorimetry (DSC) and Fourier transform infrared (FT-IR) spectroscopy. Our results revealed that the mixed amine comprised of aniline and N,N-dimethyl-p-phenylenediamine (AN/NNDPA) bearing primary amino groups in its structure was a highly effective catalyst for the room temperature curing of cyanate esters. When the cyanate ester and mixed amine were combined at a molar ratio of 100:5 and cured at room temperature for 5 days, the curing degree of BECy resin reached 79.7%. The room temperature curing mechanism of the BECy-AN/NNDPA system was investigated using pyrolysis gas chromatography-mass spectrometry (PY GC-MS). Our results showed that the formation reactions of the intermediate structure and cyclotrimerization reactions occurred during the room-temperature curing process. The activation energies of BECy and different aromatic amine systems at different heating rates were determined using non-isothermal DSC. The results further demonstrated the catalytic effect of AN/NNDPA on the cyanate ester curing reaction. BECy-AN/NNDPA cured at room temperature has suitable heat resistance and a 5% weight loss temperature (Td5) of 361°C.
ChenXLiangGGuA, et al.Flame retarding cyanate ester resin with low curing temperature, high thermal resistance, outstanding dielectric property, and low water absorption for high frequency and high speed printed circuit broads. Ind Eng Chem Res2015; 54(6): 1806–1815.
2.
WangGFuGGaoT, et al.Preparation and characterization of novel film adhesives based on cyanate ester resin for bonding advanced radome. Int J Adhesion Adhes2016; 68: 80–86.
3.
GalukhinANosovRTaimovaG, et al.Mechanistic and kinetic insights into phenol-catalyzed cyclotrimerization of cyanate esters. Thermochim Acta2022; 718: 179382.
4.
ZhouZXLiYZhongJ, et al.High-performance cyanate ester resins with interpenetration networks for 3D printing. ACS Appl Mater Interfaces2020; 12(34): 38682–38689.
5.
ZhangXYWangFZhuYP, et al.Cyanate ester composites containing surface functionalized BN particles with grafted hyperpolyarylamide exhibiting desirable thermal conductivities and a low dielectric constant. RSC Adv2019; 9(62): 36424–36433.
6.
ZhaiCHQuitevisELSimonSL. Kinetic study of curing bisphenol a dicyanate ester with ionic liquid additive. J Polym Sci2019; 57(19): 1315–1324.
7.
GoyalSForresterMJCoverdellD, et al.High temperature performance cyanate ester composites with carboranes. Macromolecules2021; 54(19): 9155–9164.
8.
ZhangYYuanLChenF, et al.Cure kinetics of cyanate ester resin using microencapsulated dibutyltin dilaurate as catalyst. Polym Bull2016; 74(4): 1011–1030.
9.
GouHZhaoYYWeiW, et al.Effects of different imidazole accelerators on curing behavior and cross-linked network of epoxy resin/phenolic resin/benzoxazine ternary system. Polym Adv Technol2021; 33(2): 610–626.
10.
UeyamaJOgawaRTsugeA, et al.Investigation of the hardener with latent and rapid curing based on phenol-amine salts for applications to cyanate ester resins. J Appl Polym Sci2021; 138(43): e51286.
11.
IzuKTokoroYOyamaT. Simultaneous improvement of mechanical properties and curing temperature of cyanate ester resin by in situ generated modifier polymer having phenolic OH group. Polymer2020; 202: 122611.
12.
KinlochAJTaylorAC. The toughening of cyanate-ester polymers part I physical modification using particles, fibres and woven-mats. J Mater Sci2002; 37(3): 433–460.
13.
GómezCMRecaldeIBMondragonI. Kinetic parameters of a cyanate ester resin catalyzed with different proportions of nonylphenol and cobalt acetylacetonate catalyst. Eur Polym J2005; 41(11): 2734–2741.
14.
LiuTLiJHXiaoJ, et al.Thermal and mechanical evaluation of cyanate ester resin catalyzed by nonylphenol and stannous octoate. J Appl Polym Sci2016; 133(40).
15.
HuoXGuoKWangF, et al.Preparation of hybrid cyanate ester resin in the presence of polysilazane and its properties. High Perform Polym2020; 33(2): 184–195.
16.
WangMWJengRJLinCH. Origin of the rapid trimerization of cyanate ester in a benzoxazine/cyanate ester blend. Macromolecules2015; 48(8): 2417–2421.
17.
BauerJBauerM. Curing of cyanates with primary amines. Macromol Chem Phys2001; 202(11): 2213–2220.
18.
BauerJBauerM. Cyanate ester based resin systems for snap-cure applications. Microsyst Technol2002; 8(1): 58–62.
19.
MaJLeiXTianD, et al.Curing behavior and network formation of cyanate ester resin/polyethylene glycol. J Appl Polym Sci2015; 132(15): 41484–41494.
20.
WangDHouDChenZ, et al.Effects of trace phenolic hydroxyl groups on the cure behaviours and properties of cyanate esters. High Perform Polym2020; 32(7): 775–783.
21.
HeJHouDMaH, et al.Preparation of phosphorus-containing cyanate resin with low curing temperature while excellent flame resistance and dielectric properties. J Macromol Sci, Pure Appl Chem2019; 56(7): 629–639.
22.
HuangJLiPHuW, et al.Improving the toughness of polycyanate ester by adding epoxy pre-polymer with different molecular weights. J Appl Polym Sci2020; 137(45): e49395.
23.
YamasakiHMoritaS. Identification of the epoxy curing mechanism under isothermal conditions by thermal analysis and infrared spectroscopy. J Mol Struct2014; 1069(1): 164–170.
24.
HuangCSunXYuanH, et al.Study on the reactivity and kinetics of primary and secondary amines during epoxy curing by NIR spectroscopy combined with multivariate analysis. Vib Spectrosc2020; 106(1): 1–10.
25.
IzuKTokoroYOyamaT. Curing acceleration of cyanate ester resin by a phenolic compound having a tertiary amino group at the ortho-position. Polym J2020; 52(11): 1245–1252.
26.
EllisonSTGiesAPHerculesDM, et al.Py-GC/MS and MALDI-TOF/TOF CID study of poly (phenyl sulfone) fragmentation reactions. Macromolecules2009; 42(15): 5526–5533.
27.
MogiRInabaMIriyamaY, et al.Study on the decomposition mechanism of alkyl carbonate on lithium metal by pyrolysis-gas chromatography-mass spectroscopy. J Power Sources2003; 119: 597–603.
28.
MogiRInabaMIriyamaY, et al.Study of the decomposition of propylene carbonate on lithium metal surface by pyrolysis-gas chromatography-mass spectroscopy. Langmuir2003; 19(3): 814–821.
29.
GuoKLiPZhuY, et al.Thermal curing and degradation behaviour of silicon-containing arylacetylene resins. Polym Degrad Stabil2016; 131: 98–105.
30.
SundariSKRishwanaSRamaniR, et al.Particulate reinforcements in dicyanate composite with nanoporous aluminum fumarate as reactive filler: thermal properties. Polymer Korea2022; 46(4): 426–435.
31.
GozkeG. Kinetic and thermodynamic analyses based on thermogravimetric pyrolysis of watermelon seed by isoconversional and master plots methods. Renew Energy2022; 201(10): 916–927.
CoatsAWRedfernJP. Kinetic parameters from thermogravimetric data. Nature1964; 201: 68–69.
34.
ClementeSPalmaARuizM, et al.Pyrolysis kinetic, thermodynamic and product analysis of different leguminous biomasses by Kissinger-Akahira-Sunose and pyrolysis-gas chromatography-mass spectrometry. J Anal Appl Pyrolysis2022; 162(1): 1–12.
35.
VazquezMMorenoIRaposoI, et al.Kinetic evolution of chalcopyrite thermal degradation under oxidative environment. Min Metall Explor2020; 37(3): 923–932.
36.
DavePThakkarRSirachR. Cobalt copper ferrite: burning rate modifier for composite solid propellants and its catalytic activity on the thermal decomposition of ammonium perchlorate. Res Chem Intermed2022; 48(2): 555–574.
37.
AliGNisarJIqbalM, et al.Thermo-catalytic decomposition of polystyrene waste: comparative analysis using different kinetic models. Waste Manag Res2020; 38(2): 202–212.
38.
GikarakisTPappasIArvanitakiP, et al.Thermal stability and kinetics of thermal decomposition of statistical copolymers of N-vinylpyrrolidone and alkyl methacrylates synthesized via raft polymerization. J Chem2021; 2021: 6633052.
39.
AkbarpourSKhoshandamBMaroufiS. Effect of V additive on the crystallization of zircon via SCS method: synthesis, characterization and reaction mechanism. Chem Phys Lett2021; 762: 138119.
40.
GuoKLiPZhuY, et al.An in situ self-catalytic hybrid cyanate ester resin and its self-catalytic polymerization behavior. RSC Adv2016; 6(83): 80213–80220.
41.
SundariSKRishwanaSKotreshTM, et al.Effect of structural variation on the thermal degradation of nanoporous aluminum fumarate Metal Organic Framework (MOF). J Therm Anal Calorim2021; 147: 1–19.
42.
ZhanXWangLZhangJ, et al.Synthesis, properties and cure chemistry of a novel room-temperature liquid cyanate ester. Mater Des2015; 88: 1100–1108.
43.
YuanLHuangSGuA, et al.A Cyanate ester/microcapsule system with low cure temperature and self-healing capacity. Compos Sci Technol2013; 87: 111–117.
