氰酸酯树脂的改性及应用研究

综述了热固性树脂、热塑性树脂、橡胶、不饱和化合物、晶须和纳米粒子等改性氰酸酯(CE)树脂的研究现状,并简要概述了改性CE树脂在工业中的应用。     

Biobased nanocomposites from clay modified blend of epoxidized soybean oil and cyanate ester resin

Novel bio-based nanocomposites were prepared by blending surface modified natural clay with epoxidized soybean oil (ESO) and cyanate ester resin (CE). A convenient method was employed to modify the attapulgite (ATT) clay by adsorbing the poly(ethylene glycol) diglycidyl ether (PEGDE) onto the clay surface, which was confirmed by the appearance of a new peak of infrared spectroscopy due to hydrogen bonding and chelation. Thermogravimetic analysis (TGA) showed that the amount of PEGDE adsorbed on ATT was influenced by PEGDE concentration in acetone solution. Scanning electron microscope (SEM) and transmission electron microscope (TEM) results showed that nanoscaled ATT dispersed well in the blend of epoxidized soybean oil (ESO) before and after curing. The thermal-physical and mechanical properties were evaluated by dynamic mechanical analysis (DMA), TGA and tensile mechanical test. The nanocomposites showed higher glass transition temperature and modulus, and the tensile strength of the nanocomposites was reinforced as compared to that of ESO/CE blends.     

氰酸酯改性环氧树脂耐热性研究

采用热变形仪和红外光谱研究了氰酸酯树脂(CE)改性环氧树脂(EP)体系的4种不同配比和不同固化温度对产物的耐热性的影响。结果表明:加入CE树脂能显著提高EP的耐热性,但固化温度对CE树脂含量不同体系的热变形温度(HDT)影响程度有明显差别。CE/EP体系中EP过量时,提高固化温度,产物的HDT显著提高,在230℃以上固化反应才能完成;两者相当或CE过量时,固化温度在180～200℃时产物的HDT最高,提高固化温度,产物的HDT反而下降。CE含量不同时,反应生成的产物各异,这是造成固化物HDT差异的根本原因。     

Modification of cyanate ester resin by soluble polyarylates

Soluble polyarylates were prepared from the reaction of 2,2‐bis(4‐hydroxyphenyl)propane (bisphenol‐A) and aromatic acid dichlorides (phthaloyl chloride and related diacid dichlorides), and used to improve the brittleness of a cyanate ester resin. The polyarylates include poly[2,2‐di(4‐phenylene)propane phthalate] (PPA), poly[2,2‐di(4‐phenylene)propane phthalate‐co‐2,2‐di(4‐phenylene)propane isophthalate] (IPPA) and poly[2,2‐di(4‐phenylene)propane phthalate‐co‐2,2‐di(4‐phenylene)propane terephthalate] (TPPA). Furthermore, a commercial polyarylate, U‐polymer, was also used as a modifier. The morphologies of the modified resins depended on the polyarylate structure and concentration. The most effective modification of the cyanate ester resin could be attained because of the co‐continuous phase structure of the modified resin: 25 wt% inclusion of IPPA (50 mol% isophthalate units, weight average molecular weight (M_w) 38 500 g mol^?1) led to a 130% increase in the fracture toughness (K_IC) for the modified resin, with retention of its flexural properties and glass transition temperature, as compared with the values for the unmodified resin. Water absorptivity of the IPPA‐modified resin was smaller than that of the unmodified resin. Copyright © 2003 Society of Chemical Industry     

Preparation and properties of maleimide‐functionalized hyperbranched polysiloxane and its hybrids based on cyanate ester resin

A new hyperbranched polysiloxane containing maleimide (HPMA) was synthesized through the reaction between N‐(4‐hydroxyphenyl) maleimide and 3‐glycidoxypropyltrimethoxysilane, which was then used to prepare cyanate ester (CE) resin‐based hybrids (coded as HPMAx/CE, where x is the weight fraction of HPMA in the hybrid). The curing behavior of uncured hybrids and the typical properties (impact strength and dielectric properties) of cured hybrids were systemically investigated. Results show that the performance of hybrids is greatly related with the content of HPMA. Hybrids have obviously lower curing temperature than CE, overcoming the poor curing characteristics (higher curing temperature and longer curing time) of neat CE, for example, the curing peak temperature of HPMA20/CE is about 65°C lower than that of CE. In the case of cured resin and hybrids, the hybrids exhibit decreased dielectric constant and loss than CE resin; moreover, the former also exhibits lower water absorption than the latter. Specifically, the dielectric loss of HPMA15/CE hybrid is only about 27% of that of neat CE resin. In addition, the hybrids with suitable contents of HPMA have significantly improved impact strengths. The overall improved properties suggest that HPMAx/CE hybrids have great potential in applications needing harsh requirements of curing feature, dielectric properties, and toughness. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Properties and structure of cyanate ester/polysulfone/organoclay nanocomposites

In this paper, a cyanate ester (CE) matrix has been modified with polysulfone and an organic montmorillonite (Nanofil 919). The blend was thermally cured in presence of copper acetylcetonate and nonylphenol. The morphology of the cured materials was investigated by wide angle X-ray, scanning and transmission electron microscopy techniques. An intercalate structure of silicate platelets in the cyanate matrix has been obtained. Furthermore, results of thermogravimetric analysis (TGA) suggest that CE/PSF/Nanofil 919 nanocomposites have higher thermal stability than the neat resin, increasing the onset decomposition temperature. Flexural strength distributions of modified and neat cyanate matrices were obtained by testing the materials in three-point bending. The results were analyzed within the framework of Weibull statistics. The flexural behavior of the resins demonstrated to be sensitive to the intrinsic flaw distribution. The modified system displayed higher fracture toughness and impact strength compared to pure CE. Dynamic mechanical analysis (DMA) studies confirmed that the PSF modified matrix developed a two-phase morphology consisting of spherical PSF dispersed in a thermoset matrix.     

Novel modification of cyanate ester by epoxidized polysiloxane

A novel modification of cyanate ester (CE) resin by epoxidized polysiloxane (E‐Si) has been developed, and the modified system is coded as CE/E‐Si. E‐Si was prepared by the reactions among octamethylcyclotetrasiloxane, hexamethyldisiloxane, (3‐aminopropyl)‐methyldiethoxysilane, and diglycidyl ether of bisphenol‐A resin. Six formulations were designed to evaluate the effect of the weight ratio between CE and E‐Si on performance parameters. Results reveal that the addition of E‐Si in CE resin cannot only significantly decrease the curing temperature of the CE resin but also improve the water resistance and toughness of original CE resin. Moreover, these positive effects increase with the increase of E‐Si concentration in CE/E‐Si systems. Thermal property investigation shows that the glass‐transition temperature and initial degradation temperature of CE/E‐Si systems are lower than that of original CE resin. For the flexural properties of the CE/E‐Si systems, the E‐Si concentration in the system exists a threshold, that is, when the E‐Si concentration is smaller than the threshold, original CE and CE/E‐Si systems have similar flexural properties, whereas when the E‐Si concentration is higher than the threshold, CE/E‐Si systems have lower flexural properties than original CE resin. All these changes of properties are closely correlated to the structure alteration from neat CE to CE/E‐Si networks. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Novel hyperbranched polyphenylsilsesquioxane‐modified cyanate ester resins with improved toughness and stiffness

High‐performance thermosetting resins should have good toughness and stiffness, so simultaneously toughening and stiffening is the main target in developing high‐performance resins. A novel modified cyanate ester resin with improved toughness and stiffness was developed by copolymerizing 2,2′‐bis(4‐cyanatophenyl)isopropylidene (CE) with hyperbranched polyphenylsilsesquioxane (HBPPSi). The mechanical properties and their nature were systematically investigated from the viewpoint of structure‐property relations using positron annihilation lifetime spectroscopy and spectral analyses. It is found that a suitable content of HBPPSi in CE resin can effectively improve toughness and stiffness. In the case of the CE resin modified with 10 wt% HBPPSi, its impact and flexural strengths are 21 kJ m^?2 and 148 MPa, respectively, about 2.6 and 1.4 times of those of neat CE resin. The flexural modulus increases from 3.0 (for neat CE resin) to 3.4 GPa. The results of dynamic mechanical analyses also corroborate the static mechanical properties. The improved toughness and stiffness of CE resin can be attributed to the synergistic effect resulting from changes of both polymer chain structure and aggregation state structure. These attractive features of HBPPSi/CE resins suggest that the method proposed herein may be a new approach for the development of high‐performance resins for cutting‐edge industries. Copyright © 2011 Society of Chemical Industry     

Environmental effects on thermoplastic and elastomer toughened cyanate ester composite systems

The effects of temperature and moisture on thermal and mechanical properties of high‐temperature cyanate ester composite materials were investigated. A resin transfer molding process was used to impregnate glass fiber fabrics with matrices that underwent thermoplastic or elastomeric toughness modifications. The elastomer‐modified material obtained the highest mode I fracture toughness values primarily because the toughener did not phase separate. Extended exposure to 200°C, however, deteriorated initial toughness improvements regardless of the modifier utilized. Although the thermal stability was increased by using thermoplastic modifiers in comparison to the elastomer‐modified material, the degradation was mainly governed by the cyanate ester network. Gaseous degradation products caused delaminations and therefore reduced strength when the materials were exposed to 200°C for 1000 h. Also, upon immersion in water at 95°C, the matrices absorbed up to 3.3 wt % more than previous values reported in the literature. Fiber/matrix interfacial phenomena were responsible for this behavior because fiber/matrix adhesion also was reduced drastically as shown by the strong reduction in flexural strength. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 556–567, 2000     

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。     

Investigation of free volume,interfacial, and toughening behavior for cyanate ester/bentonite nanocomposites by positron annihilation

Effects of filler on microstructure and toughening behavior of cyanate ester (CE)/bentonite (BT) nanocomposites with different content of BT have been studied by positron annihilation lifetime spectroscopy, X‐ray diffraction, transmission electron microscopy, dynamic mechanical analysis, etc. The interesting results found by PALS indicate that the size and concentration of the free volume holes and the apparent free volume fraction increased with increasing the content of BT, which indicates that adding nano‐layers to thermosetting materials can lead to the high crosslinking density structure “looser.” The experimental results reveal that the increases in size of free volume holes and apparent free volume fraction are related to the increasing conversion of cure reaction. On the other hand, the mechanism of toughening (by adding the nano‐clay to the thermosetting material) has been discussed by combining free volume and interfacial property. It is shown that, for the high crosslinking thermosetting material‐based nanocomposites, both the property of free volume and dispersion state of nano‐layers are the two key factors in determining toughening property. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1509–1515, 2006     

纳米CaCO_3对CE及CE/EP基体的改性研究

通过力学性能测试和扫描电镜、热重分析以及红外光谱测试研究了纳米CaCO3的加入量对氰酸酯(CE)及CE/环氧(EP)基体力学性能及热性能的影响。结果表明,适量的纳米CaCO3的加入,可有效地改善CE或CE/EP基体的韧性和强度。当纳米CaCO3的质量分数为3%时,两改性体系的冲击强度和拉伸模量均达到最大值,CE/EP/CaCO3体系较CE/CaCO3体系具有更高的冲击强度(7.8kJ/m2)和较低的拉伸模量(100.5GPa)。纳米CaCO3的加入有利提高基体的热稳定性,但CE/EP/CaCO3三元体系的热稳定性仍明显低于纯CE或CE/CaCO3二元体系。     

环氧基硅烷改性氰酸酯树脂的性能研究

采用环氧基硅烷(ESi)对双酚A型二氰酸酯树脂(BCE)进行改性,研究了ESi用量对ESi/BCE体系力学性能和动态力学性能等影响。结果表明:适量的ESi可以明显提高BCE的韧性和强度;当w(ESi)=6%时,ESi/BCE改性体系的力学性能最好,其冲击强度和弯曲强度分别从10.1 kJ/m2、94.11 MPa提高到14.49 kJ/m2、110.94 MPa;ESi/BCE体系的交联密度降至适度是其韧性提高的主要原因,并且其玻璃化转变温度(Tg)低于纯BCE体系(但降幅不大)。     

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。     

Rheological and mechanical properties of percolated cyanate ester nanocomposites

The rheological properties and mechanical properties of percolated cyanate ester monomer/layered silicate mixtures are reported. A number of different cation exchanged montmorillonites were examined in an effort to achieve maximal montmorillonite delamination. The dispersion throughout the cyanate ester of a montmorillonite with phenylated ammonium cations (2MBHT MMT) results in the formation of a percolated network. The rheology of this percolated network undergoes a viscous liquid to elastic solid transition at 4 wt% montmorillonite. The percolation of the montmorillonite in the cyanate ester results in a significant improvement in crack resistance (80%) without a sacrifice of flexural strength.     

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。     

多壁碳纳米管改性氰酸酯树脂体系的研究

针对环氧树脂(DGEBA)／双酚A型氰酸酯树脂(BADCy)体系,采用多壁碳纳米管(MWNTs)对其增韧改性,制备了MWNTs/ DGEBA／BADCy复合材料。利用透射电子显微镜(TEM)观察MWNTs在树脂中的分散情况,研究了MWNTs的用量对复合材料性能的影响,借助凝胶时间和扫描电子显微镜(SEM)对碳纳米管增强氰酸酯树脂的机理进行初步的探讨。研究表明:当碳纳米管的质量分数为1％时,复合材料的力学性能达到最佳,弯曲强度和冲击强度分别提高约15％和8％。     

酚醛型环氧树脂改性氰酸酯复合材料性能的研究

通过DSC分析,粘度、介电性能、力学性能及耐油性测试对酚醛型环氧树脂改性氰酸酯树脂复合材料的性能进行了研究。结果表明,改性氰酸酯树体系在70～160℃具有较低的粘度,理想工艺是在125～130℃下30～45min后开始加压;改性氰酸酯树脂表观活化能和反应级数分别为60.81kJ/mol和0.8846。改性氰酸酯复合材料具有良好的力学性能、介电性能和耐油性能。     

纳米碳化硅改性氰酸酯树脂研究

采用纳米碳化硅(nm-SiC)对氰酸酯树脂(CE)进行了改性,通过静态力学性能测试,TGA和DMA分析考察了nm-SiC含量对CE/nm-SiC复合材料性能的影响。结果表明,经硅烷偶联剂KH-560表面处理的nm-SiC更能有效地改善CE的力学性能和耐热性:相对纯CE,经KH-560表面处理的nm-SiC质量分数为1.00%的CE/nm-SiC复合材料的冲击强度和弯曲强度分别提高86.26%和29.56%,玻璃化转变温度由246℃提高到287℃,5%热失重温度由388℃提高到455℃。     

Combustibility of cyanate ester resins

Flaming and non‐flaming combustion studies were conducted on a series of polycyanurates to examine the effect of chemical composition and physical properties on the fire behavior of these crosslinked, char forming, thermoset polymers. Heats of complete combustion of the polymer and fuel gases were determined by oxygen bomb calorimetry and pyrolysis‐combustion flow calorimetry, respectively. Fire calorimetry experiments were conducted to measure the total heat released, the rate of heat release and the smoke generation in flaming combustion. Fire response parameters derived from the data include the thermal inertia, heat of gasification, effective heat of combustion and combustion efficiency. Halogen‐containing polycyanurates exhibited extremely low heat release rate in flaming combustion compared with the hydrocarbon resins yet produced significantly less smoke and comparable levels of carbon monoxide and soot. Published in 2005 by John Wiley & Sons, Ltd.