Phenol novolac/poly(4- hydroxyphenylmaleimide) blend hardeners for DGEBA-type epoxy resin

Phenol novolac/poly (4-hydroxyphenylmaleimide) (PHPMI) blends were used as an epoxy resin hardener. The curing behavior of the above system and the thermal and mechanical properties of the cured epoxy resin were studied. It was not necessary to use a curing accelerator for this system, because PHPMI caused acceleration of the curing reaction. The curing mechanism of this system was investigated by using model compounds. Test pieces from the neat resins and the glass fiber reinforced resins were evaluated in terms of thermal and mechanical properties, respectively. It was found that heat resistance and mechanical properties were improved by increasing the amount of PHPMI in the hardener.     

Synthesis of a novel epoxy resin containing pyrene moiety and thermal properties of its cured polymer with phenol novolac

A new epoxy resin containing the pyrene moiety in the backbone (3) was synthesized and confirmed by gel permeation chromatography and field‐desorption mass spectroscopy and infrared spectroscopy. In addition, to evaluate the influence of the pyrene moiety on the structure, epoxy resins having an anthrylene moiety (5) and having a phenylene moiety (7) were synthesized. The cured polymer obtained through the curing reaction between 3 and phenol novolac was used for making a comparison of its thermal properties with those obtained from 5, 7, and bisphenol‐A (4,4′‐isopropylidenediphenyl)‐type epoxy resin (Bis‐EA). The cured polymer obtained from 3 showed a higher glass transition temperature, lower coefficient of linear thermal expansion, lower moisture absorption, and markedly higher anaerobic char yield at 700°C of 37.6 wt %, which might be attributed to the higher aromaticity of 3 containing the pyrene moiety. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 528–535, 2000     

Thermal and electrical properties of glass fiber reinforced o‐cresol novolac epoxy composites cured with allylated phenol novolac hardener

An allyl group was introduced into a phenol novolac hardener to improve the thermal and electrical properties of glass fiber reinforced o‐cresol novolac epoxy composites. Based on ¹H NMR analysis, it was found that the degree of allylation was measured as 12.5% and 15.3% of allylated moieties underwent Claisen rearrangement. Thermal and electrical properties of the prepared composites were investigated by thermal mechanical analysis, dynamic mechanical analysis and dielectric measurements. Their thermal expansion coefficient and glass transition temperature measured by thermal mechanical analysis varied from 20.1 to 18.0 ppm K^?1 and 132.5 to 170.9 °C, respectively, due to allylation of the phenol novolac hardener. From the storage modulus at the rubbery plateau, it was confirmed that these improvements were mainly caused by an increase in the crosslink density of the matrix resin owing to allyl groups. The electrical properties of the composites, however, showed no noticeable changes by allylation of the phenol novolac hardener. Copyright © 2012 Society of Chemical Industry     

Synthesis of a bifunctional epoxy monomer containing anthracene moiety and properties of its cured polymer with phenol novolac

A new type of epoxy resin containing anthracene moiety in the backbone was synthesized and was confirmed by elemental analysis, infrared spectroscopy, and ¹H nuclear magnetic resonance spectroscopy. Thermal properties of its cured polymer with phenol novolac were examined by thermomechanical, dynamic mechanical, and thermogravimetric analyses. The cured polymer with phenol novolac showed higher glass transition temperature (T_g), lower thermal expansion, lower moisture absorption, and higher anaerobic char yield at 700°C than a cured polymer having a phenylene group in place of anthracene moiety. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 953–959, 1999     

Synthesis of a bifunctional epoxy monomer containing biphenyl moiety and properties of its cured polymer with phenol novolac

A new type of epoxy resin containing a 4,4′‐biphenylene moiety in the backbone (Bis‐EBP) is synthesized and confirmed by elemental analysis, infrared spectroscopy, and ¹H‐nuclear magnetic resonance spectroscopy. In addition, to evaluate the influence of the 4,4′‐biphenylene group in the structure, an epoxy resin having a 1,4‐phenylene group in place of the 4,4′‐biphenylene moiety (Bis‐EP) is synthesized. The cured polymer obtained through the curing reaction between the new biphenyl‐containing epoxy resin and phenol novolac is used for making a comparison of its thermal and physical properties with those obtained from Bis‐EP and bisphenol‐A (4,4′‐isopropylidenediphenyl)‐type epoxy resin (Bis‐EA). The cured polymer obtained from Bis‐EBP shows markedly higher fracture toughness of 1.32 MPa m^1/2, higher glass transition temperature, lower moisture absorption, and higher thermal decomposition temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 690–698, 1999     

气干性酚醛环氧乙烯基树脂的研制

采用交联共聚法合成了气干性酚醛环氧乙烯基树脂。研究了物料配比、阻聚剂用量、反应温度对反应的影响,测试了树脂的耐腐蚀性、气干性和力学性能。结果表明,酯化过程最佳工艺条件为:反应温度110～115℃,反应时间2.5 h,醇、酸物质的量比1.1∶2,阻聚剂质量分数0.05%,催化剂质量分数0.3%。交联聚合过程最佳工艺条件为:反应温度75～85℃反应时间2.0 h,改性剂(甲苯二异氰酸酯)加入质量5%。合成的树脂的弯曲强度为101 MPa,弯曲模量3.66 GPa,冲击强度11.4 kJ/m2,气干性、韧性、固化性能均超过同类树脂,可用于耐温强腐蚀场合以及用作表面涂层、耐温腻子基体树脂、自流平树脂等。     

Mechanical behavior of tetrafunctional/phenol novolac epoxy mixtures cured with a diamine

An amine‐cured epoxy system based on tetraglycidyldiaminodiphenylmethane and a novolac glycidyl ether resin was studied. Epoxies were prepared by varying the cure schedules and using the isothermal time–temperature–transformation diagram of the system. The materials were characterized using dynamic‐mechanical analysis (DMA), tensile stress–strain tests over a range of temperatures and testing speeds, impact, and hardness tests. Optical microscopy was used to study the fracture surfaces of the samples. Some interrelations between the behavior and the microstructure of the system are discussed. In addition, the effect of thermal aging on the mechanical properties has been studied. DMA analysis seemed to reveal a structure that tended to be less heterogeneous with increasing the crosslink density. The advance in the etherification reactions or the thermal aging has reduced the mechanical properties related with the consumption of energy to break. The optimal cure schedule according to the global properties has been established. The morphology of fractured surfaces by optical microscopy showed a clear correlation with the variation of the tensile properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2305–2313, 2000     

联苯酚醛环氧树脂固化动力学及热性能研究

以4,4'-二氨基二苯砜(DDS)为固化剂,采用非等温示差扫描量热法(DSC)研究了联苯酚醛环氧树脂(BPNE)的固化动力学。通过外推法确定了体系的固化工艺。采用Kissinger、Ozawa法计算出固化体系的表观活化能,根据Crane理论计算得到该体系的固化反应级数。采用DSC,热重分析(TGA)研究了固化物的耐热性。结果表明:BPNE的固化工艺为160℃/2h+200℃/2h+230℃/2h;固化反应的活化能约为61.86kJ/mol,指前因子为5.27×105min-1,反应级数为1.1;玻璃化转变温度(Tg)为167℃,其10%热失重温度为398.1℃,800℃残炭率为29.37%,与双酚A环氧树脂/DDS固化物相比,分别提高了22℃,11.71%。     

邻甲硼酚醛树脂固化双酚-A环氧树脂及其复合材料的性能

用邻甲硼酚醛树脂(BoPFR)固化双酚-A环氧树脂(BPAER),制备了含硼酚醛的高性能玻璃钢复合材料.分析了固化过程,研究了固化树脂以及玻璃纤维层压板的力学性能、热性能和电性能.当m(BoPFR)/m(BPAER)为1.0∶0.5时,复合材料的玻璃化转变温度从198.4 ℃下降到134.5℃,材料韧性提高.固化物有良好的耐热性能,当m(BoPFR)/m(BPAER)为1.0∶0.2时,材料在900℃时的残留率为25.83％,热降解动力学符合一级反应动力学;玻璃纤维层压板拉伸强度提高了一倍,而电性能变化不大.     

聚氨酯改性环氧树脂性能研究

采用2,4-甲苯二异氰酸酯、聚乙二醇为主要原料合成端异氰酸酯基聚氨酯预聚体,将预聚体和环氧树脂、活性稀释剂混合。用D-230进行固化,得到PU／EP增韧固化物。研究了聚氨酯不同含量对环氧树脂力学性能的影响,并用FT—IR进行了表征。用DMA研究了PU／EP固化物的阻尼性能。结果表明,加入聚氨酯预聚体明显改善了EP的阻尼性能;随着DMA测试频率的增大,tan δ-T谱向高温移动。     

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。     

腰果酚缩醛胺与环氧树脂的固化反应动力学的研究

在不同升温速率下,用差示扫描量热分析(DSC)研究了腰果酚缩醛胺固化剂(PCD)与环氧树脂的固化反应动力学。通过Kissinger、Crane方程和等转化率的方法求得了其表观活化能E=39.89kJ/mol,固化反应级数n=0.906。     

Hydrogen bonding in polyamide toughened novolac type phenolic resin

The hydrogen bonding, miscibility, and thermal stability of polyamide toughened novolac type phenolic resin were investigated. The intermolecular force of the resin increased with the content of the soft segments of polyamides (nylon 6, nylon 66) that absorb the loads in the network of brittle phenolic resin. IR (IR region) spectra and differential scanning calorimetry results confirmed that the phenolic/polyamide blend was completely miscible. Its thermal degradation temperature was higher than 400°C and increased with the increasing of polyamide content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2283–2289, 1999     

Relationship between viscoelastic properties and gelation in the epoxy/phenol‐novolac blend system with N‐benzylpyrazinium salt as a latent thermal catalyst

A study of viscoelastic properties and gelation in epoxy/phenol‐novolac blend system initiated with 1 wt % of N‐benzylpyrazinium hexafluoroantimonate (BPH) as a latent cationic thermal initiator was performed by analysis of rheological properties using a rheometer. Latent behavior was investigated by measuring the conversion as a function of curing temperature using traditional curing agents, such as ethylene diamine (EDA) and nadic methyl anhydride (NMA) in comparison to BPH. In the relationship between viscoelastic properties and gelation of epoxy/phenol‐novolac blend system, the time of modulus crossover was dependent on high frequency and cure temperature. The activation energy (E_c) for crosslinking from rheometric analysis increased within the composition range of 20–40 wt % phenol‐novolac resin. The 40 wt % phenol‐novolac (N40) to epoxy resin showed the highest value in the blend system, due to the three‐dimensional crosslinking that can take place between hydroxyl groups within the phenol resin or epoxides within the epoxy resin involving polyaddition of the initiator with BPH. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2299–2308, 2001     

New polythiourethane hardeners for epoxy resins

New mercaptan‐terminated polythiourethanes were synthesized from low‐molecular‐weight dimercaptan oligomers and diisocyanates. The characteristic bands in the FT‐IR spectra, and the specific peaks in the ¹H‐NMR spectra correlate rather well with the proposed structures of these polymers. Chemical analysis of the epoxy group conversion and swelling measurements were conducted in order to determine the crosslink densities of the cured epoxy resins. The curing characteristics and thermal behaviour of the formulated curing mixtures indicate that the epoxy/polythiourethane stoichiometry and thermal history during cure may greatly affect the curing mechanism and final properties of the epoxy networks. Mechanical studies indicated that the application of polythiourethane hardeners improves the flexibility with increasing tensile strength and impact toughness. The prepared polythiourethane hardeners have an acceptable odour and give a perfectly homogeneous system with the epoxy resins and have good storage stability with other coreactants such as diamines. Copyright © 2005 Society of Chemical Industry     

环氧树脂/改性SiC复合材料的制备及性能

采用硅烷偶联剂KH-560和丙烯酰胺对SiC进行表面改性,将其添加到环氧树脂中制备环氧树脂/改性SiC复合材料.采用傅里叶变换红外光谱仪、X射线衍射仪以及接触角测试仪探究改性SiC的性能,并对复合材料的性能进行测试.结果表明:SiC表面带有憎水基团,与环氧树脂相容性提高;SiC用量为环氧树脂质量的20％时,拉伸强度和弯...     

热引发前线聚合法固化脂环族环氧树脂

采用热引发前线聚合（TFP） 方法固化了脂环族环氧树脂（221树脂）,研究了固化剂用量、预热温度和反应器倾斜角度等因素对聚合前线的推动速率和前线温度的影响,并利用FTIR、DSC、TG等手段对固化物结构和热性能进行了表征。研究结果表明,固化剂用量越大或预热温度越高,引发前线聚合反应所需的时间越短,前线推动速率V_f 越快,前线最高温度T_max 越高,达到最高前线温度所需时间越短;试管倾斜一定角度后,下行前线方向发生偏离,V_f有所下降;FTIR测试结果表明,采用TFP法得到的环氧固化物与采用传统热固化工艺得到的固化物有相似的红外吸收,DSC和TG测试结果表明前线聚合产物具有更高的玻璃化温度和更好的热稳定性。     

叔胺催化环氧树脂/水性醇酸树脂固化行为及其性能研究

从合成的水性醇酸树脂(AR)和水性环氧树脂(ER)出发,合成了水性ER/AR树脂,用红外光谱仪、差示扫描量热仪研究了叔胺催化的固化行为;用动态力学谱仪、热重分析技术研究了材料的玻璃化转变温度(Tg)和热降解性能,测定了ER/AR玻璃钢复合材料的力学和电性能以及涂膜的性能。结果表明,N-N二甲基苄胺对该体系有很好的催化作用;材料的Tg随着AR含量的增加呈现降低的趋势,当ER/AR的质量比为5 ：5时,Tg为64.6 ℃,拉伸强度为141.67 MPa,冲击强度达到120.54 kJ/m2;ER/AR玻璃钢复合材料的介电常数在1.5 1.99之间, 损耗角正切在0.001~0.008之间;涂膜的硬度高于4H,冲击强度可达20 kg·cm。     

B‐stage characterization of o‐cresol novolac epoxy resin system using raman spectroscopy and matrix‐assisted laser desorption/ionization mass spectrometry

The B‐stage of the o‐cresol novolac epoxy resin–phenol novolac hardener–triphenylphosphine (TPP) catalyst system was characterized using Raman spectroscopy and matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry. The consistent decreasing intensities of characteristic epoxy resin peaks in MALDI mass and Raman spectra according to the melt mixing time were observed, which is due to the formation of the epoxy–phenol–TPP complex and the propagation reaction between them and with another epoxy resin. Our microscopic analysis method will provide a useful tool to control the optimum condition of the melt mixing process in the B‐stage. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1940–1946, 2000     

超支化聚合物在环氧树脂中的应用

综述了超支化聚合物在环氧树脂中的应用,简述了超支化环氧树脂、超支化环氧树脂固化剂和超支化环氧树脂添加剂的合成及应用进展,展望了其研究前景。