端羟基聚丁二烯改性氰酸酯体系固化反应动力学

采用示差扫描量热法(DSC)研究了端羟基聚丁二烯(HTPB)改性双酚A型氰酸酯树脂(BADCy)体系的固化反应动力学,根据Arrhenius方程对固化过程动力学参数进行了求解,建立了固化反应动力学模型。结果表明,随着HTPB含量的增大,动态DSC固化反应放热峰向低温方向移动,说明HTPB可以催化固化反应并降低体系的反应温度。纯BADCy和BADCy/15%HTPB体系等温固化符合自催化反应模型。纯BADCy体系以及BADCy/15%HTPB体系的表观反应活化能分别为59.67 kJ/mol、56.91 kJ/mol。     

二烯丙基双酚A催化改性酚醛型氰酸酯树脂的催化固化

研究了二烯丙基双酚A（DBA）催化改性酚醛型氰酸酯树脂（cy-5）,通过差示扫描量热法（DSC）、热重分析（TG）、冲击性能和动态热机械分析（DMA）测试,分析了改性树脂的热性能和力学性能。研究表明：DBA对cy-5有催化和增韧的双重作用,当DBA的添加量为5%（质量分数）时,催化效果最为明显,含10% DBA的改性树脂固化物的冲击强度达到7.41 kJ/m2,改性树脂固化物的玻璃化转变温度（Tg）和储能模量（E'）均有所降低,但幅度不大。     

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     

Effect of cyanate ester on the cure behavior and thermal stability of epoxy resin

Epoxy resin (diglycidyl ether of bisphenol A, DGEBA)/cyanate ester mixtures were cured with a curing agent, 4,4′-diaminodiphenylsulfone, and the effect of cyanate ester resin on the cure behavior and thermal stability in the epoxy resin was investigated with a Fourier transform infrared spectrometer, a rheometer, a dynamic mechanical analyzer, and a thermogravimetric analyzer. Cure reactions in the epoxy/cyanate ester mixture were faster than that of the neat epoxy system. The cure reaction was accelerated by increasing the cyanate ester resin component. Glass transition temperature and thermal stability in the cured resins were increased with increasing cyanate ester resin component. This may be caused by the increase of crosslinking density due to the polycyclotrimerization of the cyanate ester monomer to form triazine rings and the reaction of cyanate ester resin with the epoxy network. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 85–90, 1997     

氰酸酯/苯乙烯体系的反应性及固化树脂的性能研究

用傅里叶变换红外光谱(FT-IR)研究了氰酸酯单体的等温固化反应。获得了有机锡催化氰酸酯和苯乙烯体系在不同固化温度下的转化率和动力学参数。氰酸酯的转化率随着温度的升高和催化剂的使用而提高。不含催化剂时苯乙烯对氰酸酯的影响较小,而有机锡和苯乙烯同时存在时对氰酸酯有很强的催化作用。在所有的体系中,催化反应速率常数对氰酸酯单体浓度在动力学控制阶段表现为一级反应。改性体系的冲击强度和弯曲强度比未改性氰酸酯最高分别提高了45．3%和18．7%。     

环氧树脂/双环戊二烯双酚型氰酸酯树脂共聚体系固化动力学研究

采用Ozawa方法和Kissinger方法研究了环氧树脂和双环戊二烯双酚型氰酸酯树脂(DCPDCE)共聚体系的固化动力学,并计算了活化能、指前因子、不同温度下的反应速率常数和共聚物的总反应级数。研究结果表明,体系中加入环氧树脂后,提高了体系的反应活化能,明显降低了室温时的反应速率常数,而对固化温度(180℃)时的反应速率常数影响不大。不同环氧树脂含量的共聚体系固化反应级数均接近1级反应。     

Curing behavior and thermal mechanical properties of cyanate ester blends

Cyanate esters are a class of important thermally resistant polymers. To tailor their processability and thermomechanical properties, a series of cyanate ester blends based on a trifunctional novolac cyanate ester (HF‐5), a difunctional bisphenol E cyanate ester (HF‐9), and a reactive catalyst [2,2′‐diallyl bisphenol A (DBA)] were formulated. The effect of the blend composition on the rheology and curing behavior of these cyanate ester blends and the corresponding thermal and mechanical properties of the cured cyanate ester blends was studied. The results showed that HF‐5 contributed to good mechanical property retention at high temperatures because of its trifunctionality, whereas HF‐9 imparted processability by reducing the viscosity and extending the pot life of the formulated cyanate ester blends at the processing temperature. On the basis of the results, an optimal cyanate ester blend suitable for resin transfer molding was determined: the HF‐5/HF‐9/DBA weight ratio of 80 : 15 : 5 exhibited good processability and thermomechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4284–4290, 2006     

Influence of cyanate content on the morphology and properties of epoxy resins with phenolphthalein poly(ether ketone)

Phenolphthalein poly(ether ketone) (PEK‐C) was blended with the diglycidyl ether of bisphenol A epoxy resin and bisphenol A dicyanate ester. The effect of cyanate content on cure behaviors, thermal and mechanical properties of PEK‐C/epoxy/cyanate mixtures was investigated. As results, the increase of cyanate content slightly hindered the cure reaction of the mixtures. Fourier transform infrared results indicated that the curing reaction of the cured mixtures was complete. When the cyanate ester content increased, the flexural properties and T_g values were enhanced, and the initial thermal decomposition temperature was reduced. A significant improvement in fracture toughness was obtained when the cyanate group in the mixtures was excessive. The fracture toughness can be well explained by SEM observations. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

氰酸酯树脂/聚苯醚/纳米二氧化硅电子封装材料固化动力学研究

采用硅烷偶联剂表面处理过的纳米二氧化硅作为无机填料改性氰酸酯树脂/聚苯醚固化体系,并利用非等温差示扫描量热法研究了氰酸酯树脂/聚苯醚/纳米二氧化硅电子封装材料的固化动力学。结果表明,氰酸酯树脂/聚苯醚/3%纳米二氧化硅固化体系的凝胶温度为150℃、固化温度为181℃、后处理温度为239℃;固化动力学参数表观活化能为15.46kJ/mol、反应级数为0.82、频率因子为38174.38s-1;加入纳米二氧化硅可以降低氰酸酯树脂/聚苯醚固化体系的表观活化能,使其固化反应可以在较低温度下进行。     

Synthesis,characterization, and properties of multifunctional naphthalene-containing epoxy resins cured with cyanate ester

Multifunctional naphthalene-containing epoxy resins derived from 2,7-dihydroxylnaphthalene were synthesized and the intermediates were characterized by Fourier transform infrared spectroscopy, elemental analysis, and mass spectrometry. The cured products from naphthalene-containing epoxy resin and the dicyanate ester of bisphenol A (DCBA) exhibited a better T_g and a lower coefficient of thermal expansion than those of the commercial epoxy system. The glass transition temperature, thermal stability, and moisture absorption were found to increase with the epoxy functionality when naphthalene-containing epoxy resins were cured with DCBA. Thermogravimetric analyses revealed that the DCBA-cured system had a better thermal stability than that of the 4,4′-diaminodiphenylsulfone (DDS)-cured system. The addition of a metallic catalyst into the epoxy resin/cyanate ester system not only facilitated the cyclotrimerization of the cyanate ester but also the polyetherification of the epoxy resin. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1611–1622, 1999     

Sequential interpenetrating polymer networks from bisphenol A based cyanate ester and bimaleimide: Properties of the neat resin and composites

Blends of varying composition of a bisphenol A based cyanate ester—viz., 2,2‐bis‐(4‐cyanatophenyl) propane (BACY)—and a bisphenol A based bismaleimide—viz., 2,2‐bis[4‐(4‐maleimido phenoxy) phenyl] propane (BMIP)—were cured together in a sequential manner to derive bismaleimide–triazine network polymers. Enhancing the bismaleimide content was conducive for decreasing the tensile properties and improving both the flexural strength and fracture toughness of the cyanate ester‐rich neat resin blends. Although DMA analyses of the cured blend indicated a homogeneous network for the cyanate ester dominated compositions, microphase separation occurred on enriching the blend with the bismaleimide. Addition of bismaleimide did not result in any enhancement in T_g of the blend. Interlinking of the two networks and enhancing crosslink density through coreaction with 4‐cyanatophenyl maleimide impaired both the mechanical and fracture properties of the interpenetrating polymer network (IPN), although the T_g showed an improvement. Presence of the bismaleimide was conducive for enhancing the mechanical properties of the composites of the cyanate ester rich blend, whereas a higher concentration of it led to poorer mechanical properties due to the formation of a brittle interphase. The IPNs showed reduced moisture absorption and low dielectric constant and dissipation factor, the latter properties being independent of the blend composition. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2737–2746, 1999     

双酚A氰酸酯自聚反应机理研究

为了得到性能稳定的氰酸酯,通过傅里叶红外光谱、高效液相色谱、核磁共振等方法研究了双酚A型氰酸酯单体的自聚反应历程,并提出可能的反应方程式以期得到性能稳定的氰酸酯树脂。结果表明,氰酸酯自聚主要通过三聚反应直接生成三聚体、五聚体、七聚体等低聚物,而后体系分子质量逐渐增大形成交联网状结构,并不产生二聚体过渡结构;主催化剂并不改变氰酸酯聚合反应机理,仅是通过降低反应活化能使反应速度加快。     

环氧树脂改性氰酸酯树脂固化体系研究

采用差示扫描量热(DSC)法对脂环族环氧树脂(L2)改性双酚A型氰酸酯树脂(CE)的固化反应历程进行了研究,并探讨了L2用量对CE耐热性能和粘接强度等影响。结果表明:L2对CE的固化反应具有催化作用,但当w(L2)≥30%时,其催化效果因稀释作用而降低;纯CE和CE/L2体系在等温(210℃)固化反应过程中,其转化率在起始反应10 min内分别达到80%和91%左右;当w(L2)=10%时,CE/L2改性体系的拉伸剪切强度(22.80 MPa)和压缩剪切强度(44.40 MPa)较高,同时其耐热性能较好。     

氧化石墨烯对氰酸酯树脂固化动力学的影响

以自制GO(氧化石墨烯)作为BCE(双酚A型氰酸酯)的改性剂制备相应的改性树脂。采用非等温DSC(差示扫描量热)法、Kissinger法、Crane法和升温速率-温度(β-T)外推法研究了GO对BCE固化动力学的影响,确定了纯BCE和GO/BCE体系的固化工艺条件和动力学参数。结果表明:纯BCE体系的凝胶温度为180.0℃、固化温度为201.0℃和后处理温度为221.1℃;GO/BCE体系的凝胶温度为158.8℃、固化温度为195.7℃和后处理温度为214.3℃;纯BCE和GO/BCE固化体系的活化能分别为102.38 kJ/mol和81.68 kJ/mol,反应级数分别为0.93和0.91。     

A reaction order functional relationship with the Williams–Landel–Ferry equation in curing kinetics

A methodology is presented to obtain a kinetic model for curing reactions, from conversion against time and the glass‐transition temperature versus conversion data. Isothermal runs for a cyanate ester resin from 140 to 190°C, reported previously, were evaluated. The approach utilizes the conversion measurement time derivatives that allow following the estimated parameters' trends: the rate constant and the reaction order, in this case. An autocatalytic model was found, and the rate constants were truly constant along the experiments; thus, their Arrhenius parameters were evaluated. The methodology allowed constructing a master curve relating the variable reaction order with a temperature difference (reaction and glass transition) explained by the Williams–Landel–Ferry (WLF) equation. Four parameters describing the reaction order variation, two related to an exponential‐like behavior and two required by the WLF equation, allowed describing the whole experimental set accurately. POLYM. ENG. SCI., 54:1900–1908, 2014. © 2013 Society of Plastics Engineers     

Catalysis and kinetics of cyclotrimerization of cyanate ester resin systems

The kinetics of cyclotrimerization and the thermal stability of bisphenol Abased cyanate ester resin systems were determined using Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetry. The bisphenol A dicyanate was cured with 4 phr nonylphenol and with the octoates of zinc and manganese, and cobalt acetylacetonate at concentrations ranging from 0 to 750 ppm metal. An empirical rate law was used to predict the cyanate concentration profiles. The observed reaction rate showed a first-order dependen?e on the initial metal concentration and a second-order dependence on the cyanate concentration in the kinetically controlled regime. For the uncatalyzed systems, the kinetics was described by a second-order autocatalytic model. The thermal stability of the network was found to be dependent on the catalyst concentration for the zinc catalysts. For the samples cured with manganese, no effect of concentration on the thermal stability was observed.     

环氧改性氰酸酯树脂固化动力学的研究

采用示差扫描量热法(DSC)对缩水甘油醚类环氧树脂(E-51)与脂环族环氧树脂(R-122)共同改性的双酚A型氰酸酯(BADCy)树脂的固化反应历程进行了研究。由Kisserger方程求得共聚体系固化反应的表观活化能为60.5 kJ/mol,根据Crane理论求得固化反应级数为0.89,接近于1级反应。该体系起始固化温度为132.1℃,峰顶固化温度为168.7℃,终止固化温度为246.0℃。研究表明,环氧树脂可促进BADCy的固化,改性体系可在177℃以下实现较完全固化。     

酚类改性氰酸酯树脂体系介电性研究

采用DSC和红外等方法研究了酚对氰酸酯树脂固化反应的影响,以及不同酚含量的氰酸酯树脂体系及其复合材料在常温、高温、宽频(7~18 GHz)等条件下介电常数及介电损耗。结果表明,酚的加入可以显著促进氰酸酯树脂的固化反应;适量酚的加入能显著提高氰酸酯树脂体系的介电性但是会降低其玻璃化转变温度;含有壬基酚的氰酸酯树脂体系复合材料在宽频下表现出稳定的介电性。     

Synthesis and characterization of novel low‐dielectric cyanate esters. II

A novel cyanate ester, 2,6‐dimethyl phenol dipentene cyanate ester (DPCY), was successfully synthesized from cyanogen bromide with 2,6‐dimethyl phenol dipentene novolac, which was synthesized from dipentene and 2,6‐dimethyl phenol. For the purpose of increasing the mobility of residual DPCY during the final stage of curing and achieving a complete reaction of cyanate groups, a small quantity of a monofunctional cyanate ester, 4‐tert‐butyl phenol cyanate ester, was added to DPCY to form a cyanate ester copolymer. The thermal properties of the cured cyanate ester resins were studied by dynamic mechanical analysis, dielectric analysis, and thermogravimetric analysis. These data were compared with those of the commercial bisphenol A cyanate ester system. The cured modified cyanate ester exhibited a dielectric constant of 2.59–2.50, a dissipation factor of 0.0055–0.0089, and moisture absorption of 0.91–1.17%; these values were all lower than those of the as‐cured bisphenol A dicyanate system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 369–379, 2005     

The study on poly(ether sulfone) modified cyanate ester resin and epoxy resin cocuring blends

Poly(ether sulfone) terminated with phenolic hydroxyl groups modified cyanate ester resin and epoxy resin cocuring blends were investigated by differential scanning calorimetry, Fourier transform infrared spectroscopy, scanning electron microscopy, rheometry, and mechanical properties measurement. The results suggested that poly (ether sulfone) (PES) could accelerate the polycyclotrimerization reaction of cyanate ester and cocuring processes between cyanate ester and epoxy of modified blends because of the presence of phenolic hydroxyl groups at the end of the PES molecules. It was found that the evolution of the morphologies and complex viscosities of the modified blends sensitive to molecular weight and content of PES, the tensile strength and elongation at break of the modified blends were correlated with the morphologies of modified blends. Moreover, the evolution of complex viscosities of the modified blends also showed an exponential growth at the early stage of phase separation, which demonstrated experimentally that the coarsening processes of droplets of bisphenol‐A dicyanate and diglycidyl ether of bisphenol A and the final morphologies obtained in the blends modified with PES were affected by viscoelastic behavior. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009