一种改性氰酸酯预聚体的合成和性能研究

将聚砜树脂(PSF)和双酚A型氰酸酯树脂(BCE)在一定条件下进行预聚反应,通过红外光谱(FT-IR)、差热扫描(DSC)、扫描电镜(SEM)对所得到的预聚体树脂及其固化后产物进行分析和表征。结果表明改性后的氰酸酯预聚体具有优异的力学性能和良好的介电性能。     

Fire‐resistant cyanate ester–epoxy blends

The cure chemistry, thermal stability and fire behaviour of a series of fire‐resistant cyanate ester–epoxy blends were examined. The dicyanate and diepoxide of 1, 1‐dichloro‐2, 2‐bis(4‐hydroxyphenyl)ethylene (bisphenol‐C, BPC) were combined in various molar ratios and the reaction chemistry was monitored using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The fire behaviour of the BPC cyanate–epoxy blends was studied in flaming and non‐flaming combustion, using OSU calorimetry and pyrolysis‐combustion flow calorimetry (PCFC), respectively. Published in 2003 by John Wiley & Sons, Ltd.     

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     

氰酸酯及其改性树脂体系的反应动力学研究

利用傅立叶变换红外光谱对纯氰酸酯及其改性树脂体系进行固化反应动力学的研究。研究表明,氰酸酯主催化剂能降低反应活化能,使固化反应速度明显加快,反应温度降低;而苯酚的加入可明显提高改性体系的最大固化度。     

Synthesis and characterization of siloxane‐based cyanate ester elastomers from readily available materials: a top‐down approach

A number of siloxane‐based cyanate ester (SiCE) elastomers were prepared from commercially available starting reagents employing a hydrosilylation reaction. Each elastomer was designed to utilize 2,4,6‐tris(allyloxy)‐1,3,5‐triazine as a crosslinker and multifunctional vinyl component in the hydrosilylation reaction, ensuring that the triazine rings were completely formed, and thus the elastomers resemble fully cured cyanate ester networks. The hydride‐terminated siloxane components used were varied from small‐molecule siloxanes to pre‐polymers of different molecular weights. Attenuated total reflectance Fourier transform infrared analysis confirmed the successful hydrosilylation reaction and complete curing of the SiCE elastomers via functional group analysis. Thermal characterization by thermogravimetric analysis and differential scanning calorimetry demonstrated that thermal properties of the elastomers could be tailored depending on the type of siloxane component that was utilized. The gel content of the elastomers was also determined. Investigations into the effects of a platinum catalyst on the elastomers determined that the presence of the catalyst affected the thermochemical stability of the SiCE elastomers. Published 2016. This article is a U.S. Government work and is in the public domain in the USA.     

Examining the thermal degradation behaviour of a series of cyanate ester homopolymers

A series of thermally stable dicyanate monomers was prepared containing different thermally stable structural units, namely 2,2′‐bis(4‐cyanatophenyl)propane, bis‐4‐cyanato‐biphenyl, bis‐4‐cyanato naphthalene, 3,3′‐bis(4‐cyanatophenyl)sulfide and 3,3′‐bis(4‐cyanatophenyl)sulfone, was prepared and the identity of the products was confirmed by Fourier transform infrared and NMR spectral methods. The corresponding cyanate homopolymers were prepared and their properties were evaluated and compared. The composites were analysed for their thermal stability and thermal degradation kinetics. The series of homopolymers exhibit excellent thermal characteristics, e.g. relatively high glass transition temperatures of at least 215 °C, which were inversely proportional to the molecular weight between the crosslinks, high thermal decomposition temperature and high activation energies for the decomposition of cured resins. Determination of their limiting oxygen indices indicates that all the homopolymers are characterized as ‘self‐extinguishing’ materials. © 2019 Society of Chemical Industry     

Water uptake effects in resins based on alkenyl‐modified cyanate ester–bismaleimide blends

The analysis of cured resin blends comprising a commercial dicyanate, bismaleimide and a range of novel alkenyl‐substituted cyanates, to determine the chemical effects of long‐term exposure to water, is reported. The cured resin blends underwent accelerated water uptake by immersion at temperatures of 50 °C and 70 °C, for a period of 14–17 months. The presence of about 10–15% (by weight) of alkenyl‐substituted cyanate in the blend leads to a marked reduction in moisture absorption in comparison with the unmodified bismaleimide/cyanate blend containing a comparable amount of bismaleimide. All samples display non‐Fickian diffusion behaviour at both immersion temperatures, although this is most marked at the higher temperature. Thermogravimetric analysis was performed on alkenyl‐modified neat resin samples before and after the immersion period. The modified samples display thermal stabilities that are indistinguishable from cured resins that have not undergone immersion. Spectroscopy (near infrared Raman and mid‐infrared attenuated total reflectance) was performed on cured resin plaques to determine the sample composition as a function of modifier content. The elemental composition of the samples was also determined before and after the immersion period, and no significant variation in elemental composition was recorded for the modified samples. © British Crown Copyright 2001/DERA. Reproduced with the permission of Her Majesty's Stationery Office. Published for the SCI by John Wiley & Sons, Ltd.     

A study of the thermal and dynamic mechanical properties of functionalized aryl cyanate esters and their polymers

Differential scanning calorimetry (DSC) was employed to examine the thermally initiated and catalysed polymerizations of a number of cyanate ester monomers. Rigorous purification by preparative HPLC was found to have marked effects on the thermal polymerization characteristics of these compounds as determined by DSC. The effects on the thermal behaviour of varying the heating rate and level of catalysis were also examined. The thermal polymerization of the cyanate ester monomers was found to obey a first order model over wide apparent conversion limits. Functionalized cyanate ester/bis-maleimide copolymers were prepared and the thermal stabilities of these were evaluated by thermogravimetric analysis (TGA) alongside a variety of commercial blends and homopolymers. The dynamic mechanical properties of the cured neat resins were also investigated.     

酚酞型氰酸酯的合成与表征

采用卤化氰-酚合成法制备了酚酞型CE(氰酸酯),并采用红外光谱(FT-IR)法、质谱法、核磁共振氢谱(1H-NMR)法、毛细管法和差示扫描量热(DSC)法等对酚酞型CE的结构和性能进行了表征和分析,同时对其热性能和热解动力学行为进行了研究。结果表明:酚酞型CE的合成条件为"-15℃搅拌反应1 h→升温至5℃搅拌反应4 h→5℃保温反应2 h";目标产物失重5%温度为435℃,最大失重速率温度为453℃,表观活化能为222.49 kJ/mol,指前因子为1013.97s-1;将酚酞型CE加入到胶粘剂的基础配方中,相应胶粘剂的综合性能略高于基础配方胶粘剂。     

Triazine reaction of cyanate ester resin systems catalyzed by organic tin compound: kinetics and mechanism

The mechanism and kinetics of the thermal cure reaction of two cyanate esters (CEs), 1,1′bis(4‐cyanatophenyl)ethane (AroCy L‐10) and bisphenol A dicyanate ester (BADCy), in the presence of dibutyl tin dilaurate (DBTDL) has been investigated using Fourier‐transform infrared spectroscopy (FTIR) and High‐performance liquid chromatography (HPLC). It was found that the organic tin compound (H₉C₄)₂Sn(NCO—R—OCN)₂, an active catalyst, has high catalytic efficiency in the polymerization of cyanate esters. The consuming rate of cyanate concentration showed a first‐order dependence on both active catalyst and the cyanate ester monomer concentration. The apparent activation energies (E_a) and frequency factors of both AroCy L‐10 and BADCy were calculated. A mechanism of cyclotrimerization was proposed, based on the kinetic data and FTIR spectra, which involves the formation of an active catalyst and the catalysis of the active catalyst. Copyright © 2004 Society of Chemical Industry     

Investigation of the hardener with latent and rapid curing based on phenol-amine salts for applications to cyanate ester resins

We have developed the curing agents that have good storage stability for cyanate ester resins. It should be noted that these agents can be given rapid and efficient curing at low temperatures around 100°C. Even though the nucleophilicity was reduced by a phenol-amine salts consisting of basic aliphatic amines and weakly acidic phenols, the curing reaction with the cyanate ester occurred immediately. It means that the control of the curing reaction with cyanate esters is not easy due to the equilibrium between phenol and amine. In order to overcome this difficultly cyanate esters reactivity, the molecular motions suppression by polymer was applied in addition to the phenol-amine salts. The effect of the suppression for hardeners was studied in terms of the storage stability and reactivity to cyanate esters. It has been found out that PSM-EPEDA composed of ethylenediamine-epoxy adducts and novolac phenolic resin exhibits a large storage stability against cyanate esters by its effective suppression of molecular motions accompanied with efficient and rapid curing around 100°C.     

Synthesis and properties of novel 4,4′‐biphenylene‐bridged flame‐retardant cyanate ester resin

The bisphenol‐containing 4,4′‐biphenylene moiety was prepared by the reaction of 4,4′‐bis(methoxymethyl) biphenyl with phenol in the presence of p‐toluenesulfonic acid. The bisphenol was end‐capped with the cyanate moiety by reacting with cyanogen chloride and triethylamine in dichloromethane. Their structures were confirmed by Fourier transform infrared spectroscopy, ¹H‐NMR, and elemental analysis. Thermal behaviors of cured resin were studied by differential scanning calorimetry, dynamic mechanical analysis, and TGA. The flame retardancy of cured resin was evaluated by limiting oxygen index (LOI) and vertical burning test (UL‐94 test). Because of the incorporation of rigid 4,4′‐biphenylene moiety, the cyanate ester (CE) resin shows good thermal stability (T_g is 256°C, the 5% degradation temperature is 442°C, and char yield at 800°C is 64.4%). The LOI value of the CE resin is 42.5, and the UL‐94 rating reaches V‐0. Moreover, the CE resin shows excellent dielectric property (dielectric constant, 2.94 at 1 GHz and loss dissipation factor, 0.0037 at 1 GHz) and water resistance (1.08% immersed at boiling water for 100 h). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of poly(arylene ether) containing cyanate ester networks

A series of bisphenols containing ether linkage were prepared from halo phenol/dihalo compound and dihydroxy compounds in the presence of K₂CO₃. The bisphenols were transformed to cyanate esters by treatment with cyanogen bromide using triethyl amine catalyst. The structure of all the five bisphenols and the cyanate esters were structurally confirmed by FT-IR, ¹H-NMR and ¹³C-NMR spectral methods and elemental analysis. The cyanate esters were cured at 100 °C (30 min) → 150 °C (30 min) → 200 °C (60 min) → 250 °C (3 hr). The thermal properties of the cured resins were studied by DSC and TGA. DSC analysis shows that these cyanate esters exhibit T _g in the range of 203–234 °C. The CE(c) has the highest glass transition temperature. The cyanate ester CE(e) shows the lowest T _g which is due to its asymmetric structure. The initial degradation temperature of the cured resins was found to be in the range of 324–336 °C. The Limiting Oxygen Index (LOI) value, determined by Van Krevelen’s equation, is in the range of 35.5–38.7.     

氰酸酯和酚醛环氧改性苯并噁嗪树脂非等温固化动力学研究

以氰酸酯和酚醛环氧树脂改性苯并噁嗪树脂,制备了一种新型三元共聚树脂体系(BOZ-M/F51/BCE),并采用非等温DSC法测量该改性树脂体系的固化过程。结果表明,随着升温速率的提高,BOZ-M/F51/BCE改性树脂体系的固化工艺窗口并未发生明显的变化;BOZ-M/F51/BCE树脂体系的平均活化能为67.2 k J/mol,反应级数为0.91;三元共聚树脂体系随着升温速率的升高,达到最大反应速率对应的温度向高温方向移动。     

氰酸酯树脂结晶性研究

对氰酸酯树脂结晶性进行了研究。通过折光指数测试监控氰酸酯树脂预聚反应过程,采用凝胶色谱研究了预聚前后树脂的结构变化,通过差热扫描分析了氰酸酯体系结晶物的熔融相变。结果表明,随着预聚时间的延长,折光指数不断增加,氰酸酯树脂出现大量多聚体,结晶时间推迟;双酚E型单体的引入可降低氰酸酯树脂的熔点、增加熔限,阻止氰酸酯结晶过程。在双酚A型氰酸酯树脂中加入25%双酚E型单体,并在130℃下预聚55 m in,折光指数达1.5842时,共混体系可在室温下长时间保持液态,未出现结晶。     

大环—1,4,7,10—氮杂十二烷合成的新进展

评述了大环－１,４,７,１０－四氮杂十二烷合成的进展,比较了不同方法的优劣,介绍了大环－１,４,７,１０－四氮杂十二烷最新合成方法。     

Effect of diffusional limitations on the gelation of cyanate ester resins

The effect of diffusion control-induced unequal reactivities of functional groups on the gelation of cyanate ester resins was analyzed. By introducing differentiation into the recursive approach, a gelation model was developed to calculate the gel points of systems under diffusional limitations. Modeling results for a Zn-catalyzed cyanate resin show that the unequal reactivities have a significant effect on the gel point and the gelation is delayed to a higher conversion. However, other factors, which may include localized reactions and cycle formation, also contribute to the delay of gelation. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 115–125, 1997